1

O.., .., ..

.., .., ..

1.
2. -
3.
4.
5.
6.
7.
8.
9.

10.
11. , ,
12.
13.
14.
15.
16.
17. -
18.
19.

20.
21.
2

22.
. .
23.
24.
25.
26.
27.

1.

1.1.
1.2.
1.3.
1.4.
1.4.1. .
1.4.2.
1.4.3. .
1.5. 2+.
1.5.1. .
1.5.2.
1.6.
1.7. .
1.8.
1.8.1.
1.8.2. .
1.9. .
1.10.

1.10.1.
1.10.2.
1.11.
1.11.1. .
1.11.2.

.
. ,
.
,
.
, ,

.
,
( ),

.
,
,
. ,

.
, ,
. - .
,
, , ,
.
,

.

1.1.
,
. .
,
.
,
, .. ,
- . , (
) , 1925 .
, (, , )
, . 1925 .
(.. ) .
, ,
, , .

1924 . . , ,
,
, =h/p, h - . 1926 . .
,
(, . .)
.
,
, :
.
, -
.
,
,
, - .
,
.
( h 2 / 2m)(d 2 / dx 2 ) + V = E
- ; V - x; -
( ); ( ) , 2; m - . ,
- .
,
=(ikx), k=(2mE/)1/2.
(ikx) = coskx + isinkx, = coskx + isinkx. V=0,
,
E=p2/2m,

= (2mE)1/2.

k p=k. ,
cos(2x/),
cos(kx). , oskx ( sinkx)
= 2/k.
, : = k= (2/)(h/2) = h/.

, ,

, .
, ,
, h/p.
, ,
(-/2m)(d2/dx2)=(E-V),
exp(ikx), E=2k2/2m+V.
k = 2/

= h/(2m(E-V))1/2. ,

V -V ,
,
E=V. (E-V) - . ,

,
, , , ..
. , ,
.
.

1.2.

()
. 2.
. ,

..

(
, - .

,
,
. , dx -
,
-d; 2(r)d -
d, r
( ).
, ,
, , .
.
.
() .
= (1/a03)1/2exp(r/a0), 0=0.53 - , r - .
, ( 2)
1 3 ( 1/100
) , 0.5 , 15%
, 1
( -(1030)),
. 1
.

1.3.
, ,
, .
.
. ,
, - . ,
, ,

. 1.1 ,

.
.

, , 2dx 2d
dx d,
. ,
, , - ,
. ,
(- ),
,
, ,
,

dx = 1

d = 1

, x - , - .
, .
exp(-r/a0) (.
), .. .
, ,
, .. ,
=Aexp(-r/a0),
( N), A=N=(1/a03)1/2,

.

. , ,

, .
,
9

10

,

.

1.4.
1.4.1. .

, ( ).

. ,
2 ,
, :
( ), (
), ( ).
,
1/=R(1/n12-1/n22), - , R , n1 n2 - .
n1=1, n1=2, n1=3 (n1
). n2=n1+1 ( ), n2=n1+2 (
), n2=n1+3 ( ) .. ,
.
,

, 1.1
.
,
, .
1. ,
, n, l m. n
, .

10

11

l m ,
. l
, m -
, - .
,
,

n = 1, 2, 3 ...;

l = 0, 1, 2 ... (n-1);
m = l, (l-1), (l-2), ..., -l.
2. , ,
, , , ,
( ) ,
n. n
. (, n = 3 l 0, 1 2,
.)
, En = R/n2.
, ,
,
n2 R/n22 n1 R/n12,
h .
, h = R/n12-R/n22,
.
,
, ( )
. (r) ,
d
r [(r)]2d.
[(r)]2
.
. 1.1
:

. ,
, , , 2, .
11

12

,
.
, , .
,
, .
,
,
,
. ( n=1
: l=0, , , [l(l
+1)]1/2 .) ,
,
. .
,
, .
,
, (. 1.1).

.
,
.

12

13

. 1.1.
.

s-. s (n=1, l=0, m=0) 1s-. n=2

l=0, 2s-. , 1s-,
. -, (. 1.2),
,
,
. ,
, , .

13

14

,
, ..
. , 2s- 1s-
, 2s- , ,
, 1s-.

s-: 3s, 4s ..

1s
( )

2s
(1 )

3s
(2 )

2pz
( )

3pz
( )

3dxz
( )

. 1.2. . n=1
. n=2 ,

n=3 - ..

(
) s- , - ,
d- ..

n=0, , l, ,
n=2,
0 (2s-) 1. l=1, . n=2 l=1 2-. 2s-
,

14

15

(2)1/2.
(. 1.2), , ,
( ).
.
s- , -
.
.
1/r2 r - , ,
, J2/r3 (J - ).
, J0, r
.
l=2, d-, l=3 (f-)
(g-, h-, j-). , - , l0,
, ,
.
2- , 3- .
,
( , .
1.1), . 1.2. - ,
. ,
, ,
, .
- , .. ,
, , , ,
. ,
, .
- l=0, m
+1, 0 -1. m
. - m=0
z (. 1.2),
pz-. pz - (. . 1.1 1.2) ,
z.
, ,

15

16

.
x y (. . 1.1), px py.
n=3, l 0, 1 2.
3s-, 3- 3d-. 3d- ,
l =2 m 2, 1, 0, -1 -2. 3d . ( 4d ),
(. . 1.2).
,
,
. ,
2s- , 2-.

.

.

1.4.2.
,
, .. ,

(,

-)

( ) .
,
.
( 1.5),
.
, .
, ,
? :
16

17

, ,
()
. ,
.
,
, .
, , 1s-
0=0.53 (53 ). 2 s-
2.76 (276 ). ,
, .. , .
(Z)
53 /Z, Z - .

He

Li

Be

Ne

0.53

0.26

0.18

0.13

0.11

0.088

0.076

0.066

0.059

0.053

1s-

()

, 1s- 6 1s-
.

1.4.3. .

, ,
, ,
.

( ).
,
,
, .

17

18

1
1s, .. 1s-. .
(Z=2) ,
1s-, 1s-
, .. ,
(
+ 0/Z=0.53/2=0.26 ).
, ,
, 1s-.
1s2 ( 1s). ,
, .
,
,
, 1s-. ,
- ,
. , ,
1s2,
1s-, - .
1s-,
, .
, .
,
: s=1/2. ,
, ,
; , .
1s-
.
z ms, ms +1/2 (-),
-1/2 (-). , 1s- -

(n, l)-.
18

19

, - -, .. , , .
1s-,
(Z=3). 1s, ,
- .
,
:

, ,
. ,
.
,
1s-,
.
n=2. 2s- 2? ,
( ),
. ,
( 1s-) , , ,
. s-
, -
. , 2s-,
1s-,
,
3- .
, 2s 2-. ,
n=3 3s<3p<3d -
n=1 n=2. ,
. , 3-

, 3s-.

19

20

, ()
1s22s.

Z,

1s<2s<2p<3s<3p<3d<... Z
, ,
. , 1s-,
2s- .., 2, 3 .. , 3d, 4d
.. - , 4f, 5f .. - .

.
H

He

Li

Be

Ne

1s

1s2

1s22s

1s22s2

1s22s2

1s22s2

1s22s2

1s22s2

1s22s2

1s22s2

2p

2p2

2p3

2p4

2p5

2p6

1.5. 2+.

,
.
- 2+. -
,
.

1.5.1. .
2+. - .
, . 2+.

. 2+.
-, ,
( 2000 ) .
, ,
20

21

, -
. ,
1 , 1 , ,

, . ,
. -
, ,
, , , ,
,

..

_-

2+.,
( ) -
.

(1/rA+1/rB), rA rB - .
, 1/rA>>1/rB,
,
1s (1sA).
,
,
1sB.
:

1sA+1sB.
,
().

, . .

d r 2(r)d,

(1sA+1sB)2d =(1sA)2d +(1sB)2d + 2(1sA)(1sB)d.
1sB (. 1.3),
(1sA)2;

21

22

(1sB)2.
, 1sA 1sB
.
, ,
(.. (1sA)2 ), ,
, ((1sB)2) ,

2(1sA)(1sB)d,

2d. ,

,
(. 1.3).

. 1.3. ,

, - , ..

. 1sA 1sB,
,
. ,
.

,
.
22

23

. , ,
2+., ,
.
,
, .

- ,
,
.
, , 2+.
.
,

, ,
-
.

1.5.2.

(1sA+1sB)-

() , ..
.
,
. . -,
,
, . -,
,
.
;

(. 1.4). (),
R,

23

24

( ; 2+.
R=1.06

).

(1sA+1sB)-

,
.

. 1.4. 2+.

2+.,
, , 1sA 1sB
(. 1.5). 1sA-1sB,
1s-1s,
.
() ,
, 1sA-1sB-, .

(1sA-1sB)2d =(1sA)2d +(1sB)2d - 2(1sA)(1sB)d.

24

25

,
, ..
(. 1.5). , , 1sA
1sB ,
, . , (1sA-1sB), . ,
, ,
,
. (1sA-1sB)- (
- ).

1.5.

. 1.6.

()

, 1s-

(),

. 1.4.
. 1.6
R.

( s); (*) -.

25

26

,
: , ,
, , , -
. ,
, .. .

. 2+.
:
HA

HB

HA

HB

HA

1sB

1sA

HB

2+.

HA
1sA

HB

HA

HA

HB

HB

1sB

2+.

1sA 1sB ,
- .
,
. ,
, , ..

.

1.6.
1.4.3 ,
.
. ,
2+., ,
, ,
. ,
2, XY.

26

27

2.
: 1s

1s*.

,
(. 1.7, ). 1s2.
,

,
. ,
,
.
, ,
,
, 2.
.
1s*
H1s

H1s

He1s

1s

He1s

He2s

He2s

He1s

He1s

. 1.7. 2 (), 2 () ...* ()

2. , 2 .
1s 1s* 1s

,
1s-. ,
, 1s*- (. . 1.7,).
() ,
.
1s*-. 2 ,
.
2

.
27

28

, .. ,
, , 2
, .

(, 1s- 2s-).

1s21s*2s, 2s -
, 2s -.
1s*- ,
1s2 (. 1.7,), ...* ,

. ()
.
2- 2-. 1s-
(. 1.4.2),
, ..
.

2s-

,
. 2s- 2. .
2-,
,
(. 1.8,).

.
, - .

, 2- 2*-.

28

29

2p*

2p

2p

2p*

2p

2p
2p

2p
2p*

2p

2p*

2p

2p
2p

. 1.8. 2- () 2*- (); -

, - .

2- -,

,
( , . 1.8,).
-, -.
2-
2*-. , -,
.
, .
1.8,.

2-

2-

.
. 1.8,.
,
.
2- 2-
:

29

30

A
2pX
2pA
A

. .
. .

2pZ(A)

B
2p*-MO

2pX

2p-MO

2pB

. .

B
2p*-MO

2pZ(B)

. .

2pMO

s,p-. s- , sp .
:
.
,
, .. , .
N2, O2, F2 2s- ,
2-. , , 4,
NH3, 2 , sp-,
. 1.9,; -. - ,
s- - , -
.
, ,
, . 1.9,.
, (
) , ()

, .. .

30

31

2p*
2p

2p*

2p

2p
2p
s

px

2s*
2s

2s
2s

pz

1s

1s*
1s

1s

. 1.10.

. 1.9. sp-

.
. . 1.9, , s- -,
,
, . 1.9, s- , pz- .
, .
. . 1.10
, -
. ,

, ,
.
.
.
. N2 14 .
1s-.
,
1s*-. 4
2s- 2s*-. 2 , ,
2-, - 2py-,
31

32

, 4 . ,
12

2-.

N2 1s21s*22s22s*22422.
, ,
. 1s .
1s*,
. 2s-
2s*-. 2- ,
2*-; 2-.
, ,
NN.
. 2 16 , ..
, N2.
2*-.

1s21s*22s22s*224222*2. , 2
, =.
, =,
, - . .
, : 2*-
(. . 1.10) ? ,
2x*2y*, 2x*2,

.
( 2x* 2y* , ..
), . ,
, ,
. ,

, , 2

32

33

, .. 2 .
: .
, ,
, . 2
.-..
,
, , - .
, ,
,

2-,

2x*-, - 2y*-.
:

- + ""
-

,
: -
-.

1.7. .
, , -,
, , , . 1.10
.

. :

,
, - .
+-,

33

34

,
;
, -
. HF,
H+F-.

, , .
,
.
,
(. 1.1).

. ,

=+,
- ,
, - ,
. ,
.. 2, 2. (. . 1.3.)
.
2=2=1/2, 2+2=1, +- 2=0
2=1. +- 2<1/2, 2>1/2.
HF. F

2s

F2s,

, ,
-, ,

CF>CH. ,
( -) ;
CF CH H+F-,
CF2 CH2.
34

35

HF

F1s

H1s

, HF F, .
HF
, s-,
H1s F2p:
H

F
(1s2p)

F2p

H1s

F,
. H F
s- (. . 1.17).
1.1
()
H
2.20
Li

Be

0.98

1.57

2.04

2.55

3.04

3.44

3.98

Na

Mg

Al

Si

Cl

0.93

1.31

1.61

1.90

2.19

2.58

3.16

Ca

Ga

Ge

As

Se

Br

0.82

1.00

2.01

2.01

2.18

2.55

2.96

Rb

Sr

In

Sn

Sb

0.82

0.95

1.96

1.96

2.05

2.66

1.8.

35

36

1.8.1.

,
,

,
, . LiH
. 1.11.

Li2p
Li2s

H1s

Li1s
. 1.11. Li .

Li2s H1s, Li2p.

H1s-Li2s.
, :
=1(Li2s)+2(Li2p)+3(H1s)

. Li-H , Li
. , -
Li- . , 1s- , 2s-
2-
, :
Li-H

Li-H
+

H1s

.)

Li-H

Li2p

Li2s

.)

-,
Lih1

Lih2,

, -

36

37

s- -

, - .
+

(Lih1)

(Lih2)
Li2px

Li2s

,
H1s , ..
=C1(Li, ) + 2(H1s).

, Lih2,
:
Li-H

Li-H

+
H1s

Lih2

.)

(LiH)

, *- Li-
1s- .
Lih1,
. , ,
,
.
Li-H

Lih1

(.

Li-H

Li-H
H1s

(LiH)

, * ,
.

:
, .
.

37

38

,
.
, ,
, - , .

1.8.2. .
sp3-. 4

.
1s22s22p2.
, 2- 2 . ,
2,
. , ; ,
(.. 5).
,
1s22s2p3, ( 2s
2) . 2s 2-, , ,
-
[C(1s22s2p3)+4H(1s)CH4].
s - -
sp3- (h1, h2, h3 h4),
:
h1 = 1/2 [(s+px)+(py+pz)],
h2 = 1/2 [(s+px)-(py+pz)],
h3 = 1/2 [(s-px)+(py-pz)],
h4 = 1/2 [(s-px)-(py-pz)]/

38

39

x
h2 y

h1 y

px-py-pz

px+py+pz

x
h3

h4 y

-px+py-pz

-px-py+pz

.1.12. sp3- .

sp3-

, ,

. . 1.12;
-,
, s-
,
.

.
, ,

..

39

40

, NH3 2. NH3
2 .
,
:

..
N

..
..

H
, , , HNH NH3 107,
2 - 104.5, .. ,
( 109.5). , NH
NH3 2 .
,
NH ,
,

-, . 2, ,
.

.
sp2-. () 2=2

= - -. -
-
, 1s22s2p3. 2s-
2- sp2- ,
,
, .. 120.
:

h1 = 1 / 3s + 2 p x
h2 = 1 / 3[ s + 2 ( p x cos 60 o + p y cos 30 o )]
h3 = 1 / 3s 2 ( p x cos 60 o p y cos 30 o )

40

41

sp2- .
1.13, - .
y

y
s

px
x

h1

30o

y
s
x

h2

(-pxcos60o+pycos30o)

30o

s
x

h3

(-pxcos60o-pycos30o)

y
120o

120o

. 1.13. sp2- .

,
22.
:

(
)

-

, ..
=-. ,
41

42

-, .. ( 90
) -. - 65 / -
, .
sp-. ()

, .
sp- ,
-:

sp-
(
)

- , sp-
:
h1 =

1
(s + px )
2

. 1.8.1 LiH.
sp- ,
.

1.9. .

,
, ,
.

.
, - ,

42

43

:
,
.

+431 /

+402 /

-304 /

-538 /

. 1.14. 4.
.
.
, - .

. . 1.14

: (1-4) (58). .

. , 1
. . 1.14
, 1 .
, 1, ,
, . 1
2, 3, 4.
, .
43

44

2 ,
; (

).

;
(). , 2 3
: ,
. 4 ,
;
.
5,
6, 7. . 1.14,
, 2, 3, 4, .. : -
. 8,
4.
(. 1),
.
,
.

, 1,
, , - 2, 3, 4,
, ,
.
,
. ,
.

13 23 3, , , .
1.14, , ..
: 13 2, 3, 4,
23 - 1.

44

45

, , 4
, -, sp3 1s- ,
.
,
.
,
. ,
;
.
, . 1.14,
,
. ,
,
2. 4
. 1.15. , ,
. , 1 8
2s H1s, 2, 3, 4 H1s, 5, 6 7 -
2 H1s. . 1.14 1.15 ,
,
.

,
.

4
1s- .
45

46

. . .
. .
8
.

. .
. .
5
.

. .
. .

. . .
. .
6

.
3

. . .
. .
7
. . .
. .

.
.

. .
. .

. 1.15. 4,
. . . 1.14.

HF. . 1.16

HF.
2s- 2- ,
1s -,
. 14 , .
, ,
, ,
.

46

47

(H1s-F2p)

5
F

( " ")
( F2)

H
3

c
(2H1s+F2p)

2
F

(2H1s+2s)

. 1.16. HF

(3 4)
; -,
.
, F,
.
F ,
, .
, , 1 (. 1.16),
,
, - .
HF ,
,
. , , H+-F-,
.
HF. - 1
H1s F2s,
H1s F2 ),

47

48

H1s F2s. .
, H-F H1s
F2s, H1s F2p. ,
1.8.1 LiH. -
(. 1.1.), , ..
, .
- H1s F2,
.
2 3. F2s H1s
, ,
. 1 2s-
(. 1.16). 2.
: 2 NH3.

(. 1.17) , .
HF, 2 .
,
. ,
, .
, ,
.
H

H
O
H

H
H

H
H
H

48

(" " 2)

(" " 2p+2H1s)

(2H1s+O2p)

(2H1s+O2s)

O
H

(2H1s-O2s)

H
H

(H1s-O2p-H1s)

49
. 1.17. 2

NH3 (. 1.18)
. - ; ,
, .
N

H
H

N2p

H
H

(2H1s+N2p)

H
H

(H1s+N2p-H1s)

H
H
(3H1s+N2s)
H

. 1.18. NH3.

HF, H2O, NH3

() -,
. (. 1.16-1.18)
: NH3 (-230) > H2O (-260) >
HF (-410 /). ,
NH3, , ,
.

.
-.

2=2.
, ,
()
-.
,

49

50

-. . 1.19,
.

-. ,
, , * (. . 1.19), ,
.
, *- :
-, *-.
,
(, ) - (),
(, )
*- (). ,
.
, ,

.
1981 . ..

, SN2,
-, 1,3- ,
, ..
.

()

50

(/)

51

+535

+506

+378

+364

+343

*cH2
*cc, *cH2

*cH2, *cc

*cH2

*cH2

*cc ()
+150
cc ()
-230

-320

*cH2
cH2, cc

-350
cH2
-401
cH2
-450
cc, cH2
-634

. 1.19. .

,
() ,
, -
(. 1.20). (-260 /),
(-230 / ), ,
, .
,
.

()

51

(/)

52

()

()

+200

-260
cc, cH
-410
cH
-470
cc, cH
-630

. 1.20. .
.

- ,
, ,
. ( ,

),

(. 1.12).
1, . 2
, - . ;
- 2,
. 2
. ,

( ). 3
, .
, -,
, 1,3- - (. 1.22).

52

53

, , 1,3- -
.

( )

()

3
(-

2
()

2
()
. 1.21. - ,

-, ,
, , 1,3,5- ..,
- ,
, (, )
2.
12.

53

54

()

(/)

+180

+82

-230

-300

. 1.22. -

1.10.

1.10.1.

.
,
.
1931 . . ,

, .

54

55

( )

, 1963 . . -
().

. ,
,
- ,
.
.

(. 1.1),

=

(1.1)

- (); -
(

),

. ,

. , ,
d/dx,
, .. d/dx(ecx) , .. , .
, .
, x d/dx, d/dx()
x. .
(1.1)
.
, .
, , ,
(
).

:
i = Cij ij ;(i = 1,2,3,..., n; j = 1,2,3,..., n)
j

55

(1.2)

56

Cij - j; i -
; j - ; n - .
, - (n=3) - (.
. 1.22):
2
1

1=121+122+133,
2=211+222+233,
3=311+232+333.
,
.
, ,
, , ,
.
, .
1. (1.1) .
, LL2, L (, xd/dx(x)d/dx(x2)). - , ,
=2
2. :

Hd = E d
2

E=

Hd
d

(1.3)

, , (1.3),
, 0, -
, .
,

56

57

E=

Hd
0
d

(1.4)

(0) Cj
( = C j j ; (1.2)) ,
j

. ,
:

E
= 0.
Cj

(1.5)

Cj (Ei),
(1.5) ,
(1.2). , (1.2)
(1.4), (j) ,
E=

( C
j

) H ( Ck k )d
k

( C )( C
j

)d

C C H
j

C C
j

H
i

d = H jk

d = S jk ,

C C
E=

Hjk

C C Sjk
j

x
.
y

(1.6)

, (1.5),

E
=
Cj

x
y
x
Cj
Cj
y2

=0

(j= 1, 2, 3, ..., n),

(1.6)

x
y
E
= 0.
Cj
Cj

(1.7)

x y (1.6) j,
57

58

x
= 2Ck H jk ,
Cj
k
y
= 2Ck S jk
Cj
k
(1.7)

C
k

( H jk ES jk = 0 (j, k = 1, 2, 3, ..., n).

.
,
(1.2), . -,
j k 1 3 j
,
C1 ( H11 ES11 ) + C2 ( H12 ES12 ) + C3 ( H13 ES13 ) = 0

C1 ( H 21 ES 21 ) + C2 ( H 22 ES 22 ) + C3 ( H 23 ES 23 ) = 0
C1 ( H 31 ES 31 ) + C2 ( H 32 ES 32 ) + C3 ( H 33 ES 33 ) = 0

(1.8)

(1.8)

H jk ES jk ( 1.9) .
(1.8) ij. Hjk
Sjk , .

. -

, .

2
() ()
.
H11 ES11
H 21 ES 21
Hjk-ESij=
....
H n1 ES n1

H12 ES12
H 22 ES 22
....
H n1 ES n1

.... H1n ES1n

.... H 2 n ES 2 n
=0
....
....
.... H nn ES nn

(1.9)

. ,

, -, :
1) Hjj = ;

58

59

2) Hjk = , j k ,
Hjk = 0, j k ;
3) Sjj = 1; Sjk = 0 j k;
4) - , ,
-.
, ,
2-.
, , Hjj ,
; -
.

j k.
, , ,

. , (. 1.23)
,
,
.
Sjk ; j=k 1.
j2 d = 1 ( ; . 1.3),
, Sjj =1, . , Sjk = 0
jk, , (k = j +1), (
, Sjk = 0.25).
- , - , - , .
,
,
. : -

, ., ,
, ,
( -).

59

60

, -
(1.8) (1.9)

E
= 0.
0

E
= x,

:
x 1 0
1 x 1 = 0.
0 1 x

(22)-
,
: j- ,
j- :
x 1 0
1 x
1 1
x 1
1 x 1 =x
1
+0
.
0 x
0 x
1 x
0 1 x

,
. (22)
:
x 1
1 x

= x 2 1.

x ( x 2 1) 1( x ) = 0 ,
x = + 2 ,0 - 2 .

-,

2 , 0 - 2 ,

.. 1.41, 0 -1.41. , ,
(1.5; 0 -1.5; . . 2.11 .2).

60

61

E = ni E i
i

ni = i. ,

E = 2( + 2 )

E = 2( + 2 ) +

E = 2( + 2 ) + 2

2 .
, - .
()

=n(+)+ni,
n - ( n = 2), ni ( - 0, - 1,
- 2). , - ,
= - = 2( 2 -1) = 0.82.

C
i

2
i

= 1.

1 + 2

= 0,

1 + 2 + 3 = 0,
2 + 3= 0,
=

2 , 0 - 2 . = - 2 ,

- 2 C1 + 2
1 -

= 0,

2 C2 + 3 = 0,

2 -

2 C3 = 0.

61

62

2= 2 1.

1 = 3.

C12 + C22 + C32 = 1.
, 1 = 1/2, C2 = 1/ 2 C3 = 1/2.
, -
1 = 1/21 + 1/ 2 2 + 1/23.
= 0 =

2 -.

1.10.2.

1931 .
,
.
,

.
-.
.

: ,
, .
.
- ,
15-20 100-150 .
,
.
, ,
(H, C, O, N ..) ,
.

62

63

(), (),
-, -,
,
,

. : CNDO
(., 1965), , ,
, ; INDO,
, MNDO
(., 1975),
, AM1 (
), PM3 (
), ZINDO (

).

(), 1927 . .
... -
()
.
( )
.
, , ..,
.
(), , ,
.. ,
.
- .

() , .
, ,
- ..
,
.
, .

63

64

(,
s- - d-)
,
.
,
. ,
-.
,
, (
- - ),
. ,

.
, .
,
,

. ( )

.

. ,
-,

-.

.
0.
0
.
,
- ..

,
.

64

65

( )
.
---,
. -
, .
-

..

.
.
, ,
.
-

, ,
, ,
.

.
(), ().

65

66

, .

(DFT).
, ,
( 3). DFT
, ,
,
.

1.11.

1.11.1. .

, ,
,

;
- ,
, .
, .

,
.

,
.
2.
1s22s2 (. 1.4.3).
,
( n=2) 2s 2.

66

67

,
1s22s2. ,
2 : {Be2s, Be2p HA1s HB1s} (
). , .. {Be2s,
Be2p, HA1s, HB1s} .
:
. ,
:
= [Be2s(1)][Be2p(2)][HA1s(3)][HB1s(4)]

.
,
.
N ,
, N/2 - -.
,
, . 2
:
1

HB
4

3 1

HA
3

Be

(I)

(II)

(
,

(III)

,
- (), .
(n) ,
-,

67

68

n=

N!
,

N N
! + 1 !

2 2

N - . 2 N=4, .. n =2,
, .
? , ,
, (I) (II),

--.

(III)

,
2, .

..

Be

= (CII + CIIII),
,
. Be2s HA1s 2 H1s
(I) . (II) 2HA1s Be2s-H1s, (III) - Be2s-2 HA1s-H1s.

1.11.2.

. , H-F Na-Cl
.
, .
, ,
, ,
:
H+F-.

68

69

HF
,
.
H-F F,
, F HF -,
- .

HF

- :
H-F H+F

( HF
), ,

. ( , . 1.1,
, H-F 40%).

., ,
30-50- . ,
,
,

. ( )

, .
, ,
,
, ..

;
.

. ,

69

70

, ,

.

.

( )

R2C-PR3

O
O

R2C=PR3

(-)

CH2=N=N

R2C

()

CH2-N=
O

()

C2=
O

R2C

R'

R'

,

. ,
.
, IV V ,
,
.
H3C

H3C

(IV)

(V)

,
,
.
,

70

71

,

(. . 1.11.1).
.

, -
,
.
,
,
.

, VI VII.
A

F
E

D
(VI)

B
C
D
(VII)

A, B, ..., F, - 1, 2, ..., 6, - (1)(2)+(2)(1),

( , 2-).
- C(3)D(4)+C(4)D(3), - E(5)F(6)+E(6)F(5).
VI
VI
BC
= [(1)(2)+(2)(1)][ C(3)D(4)+C(4)D(3)][ E(5)F(6)+E(6)F(5)].

( , ).
, ,
-:
- -
(, ). ,
VII:
VI
VII
= BC
+ BC
.

71

72

,
VII (1)(2)+(2)(1) ..,
VI

BC
VI
VII
- . BC
BC

.

VIII-X. ,
, ,
6%, - 40%.

VIII

IX

XI
XII

. XI
XII, ( ),
, .

: .
, -
(N=6, ,

n=6!/[3! 4!]=5). ,

.

" "(
"" )

,
.
(
).

72

73

.
,
,
.
,
,
. , = 1.22 , 2
- 1.15 , .. ( 1.10 ).

==,

( ):

==

_
=-

_
-=

.
,
, .

(. . 2), .
,
.
2.

-
2.1. .... 74
2.1.1. ....................................................................................... 75
2.1.2. .................................................................................................................... 77
2.1.3. ....................................................................... 79
2.1.4. -- .............................. 81
2.2. ................................................................... 85
2.2.1. ................................................................................ 86
2.2.2. ............................................................................................................. 92

73

74
2.2.3. ......................................................................... 101
2.2.4. ....................................................................................... 102
2.2.5. ...................................................................... 104
2.2.6. ................................................... 106
2.2.7. ................................................. 110
2.2. ......................................................... 112
2.3.1. - .......................................................................................... 113
2.3.2. ............................................................................................................... 115
2.3.3. - .................................................................................. 116
2.3.4. ............................................................ 118
2.3.5. ....................................................................... 120
2.3.6. ....................................... 125
2.3.7. ........................................................................................................... 127
2.4. - ....................................................................................... 129
2.4.1. -............................................................................ 130
2.4.2. - ...................................................................................... 139
2.4.3. ......................................................................................... 142
2.4.3.. .................................................................................................... 144
2.4.3.. ............................................................ 145
2.4.4. -, .............................................................................. 154
2.4.5. .......................................................................................................................... 161
2.5. - ....................................................................................... 162
2.5.1. - ................................................ 162
2.5.1.. HF ........................................................................................ 162
2.5.1.. ..................................................................................................... 167
2.5.1.. ................................................................................. 170
2.5.2. ................................................... 174
2.5.2.. ................................................................................... 177
2.5.2.. ................................................................................ 179
2.5.2.. ............................................................................ 182
2.5.3. .................................................................................................................... 184
2.5.4. ,- ................................. 189
2.6. " " "
" .............................................................................................................................................. 191
2.6.1. - ....................................................................... 192
2.6.1.. .................................................................................................................. 192
2.6.1.. .................................................................................................................... 196
2.6.2. " "......................................................................................... 200

2.1.

. ,
.
, ,
,

74

75

,

.
.
,
.

2.1.1.

(+q) (-q) R,

qR. , CH3F

, .. ,
, (,
3) - . ,

CH3F

C-F.
, ,
.
CH3

+q

-q
R

= qR

() (), 1=3.336.10-3
..
,
, ,
.
, ,
,

, .

75

76

. -,

, . -,

.
R ,
0R, 0 -
(8.854.10-12 -1.2.-1); , ,
1/40R, - ( 0 )

,
. , =78;
,
.


( ). ,
,
.
. 2.1.

2.1

.1024, 3

l4 ( )

10,5

CHCl3 ()

1,01

8,50

CH2Cl2 ()

1,57

6,80

CH3Cl ()

1,87

4,53

CH4 ()

2,60

CH3OH ()

1,71

3,23

CH3CH2OH ()

1,69

76

77
C6H6 ()

10,4

C6H5CH3 ()

0,36

o-(CH3)2C6H4 (-)

0,62

He

0,20

Ar

1.,66

2.1.2.

, .
, ,
,
, .
=0, -
, .

(3 3)
(. 2.1). ,

, .

N(+2/30kT)=3(-1)( +2),
N - ; - ;
0 - ; k - ; T . ,
1/T, 2/30k
- , ,
1/T =0, - . ,

,

,

77

78

( )
.
, .
. ,

.
,
.

. ,
.
,
, ,
. ,
. Z.
,
, , .
-
. - , - -
. ,

,
.
-er, r - , e - , ,
,
er. ,
I (..
, ),
er(erE/(1/2I)), (-er)
, erE/(1/2I). ,
2e2r2/ 0I, Z,
,

78

79

2Ze2r2/ 0I.
, ,
(.. ),

. ,
. , , ,
. ,
, , .
, -,
, - (

-).

. ,
, (. 3),
(. 3),
(. 9) ..

2.1.3.

.
, .

. , ,
-- . : 1)
-

,
,

2)
3)

- ,
.
,
- ,
,

79

80

. --

R6,

..

. , -
.
,
.
, ,
(
) (
).

,
.
,
, ,

,
.
,
. ,

, ..
,
.

, ,
,
, .
,
1*,
, 2*. 1* 2*
. 1*

80

81

, ,
. ,
, .
--

V = -C6/R6,
V - ; R - ; C6 - ,
.

R-6, -
, .
,

.

2.1.4. --

,
. ,
,
, ,
. ,
(
), , ,
2 (. 1, . 1.6), ,

. ;
,
.

81

82

)
.
,
. ,

, .
2.2
-- (R) (R) ( )

H-

1.20

0.30

N-

1.55

0.70

F-

1,47

0.64

N=

1.55

0.60

Cl

1.75

0.99

1.60

0.55

Br-

1.85

1.14

P-

1.80

1.10

I-

1.98

1.33

As-

1.85

1.21

0.77

0.665

O-

1.52

0.66

C-

1.70

O=

1.50

0.55

C=

1.77

S-

1.80

1.01

1.78

0.60

Se

1.90

1.17

Si

2.1

1.17

Te-

2.06

1.37

. 3- -2-, ,

SiH3-

82

83
2.3
()
sp3-

sp2-

1.09

1.54

sp -

sp-C

Si

Cl

Br

1.08

1.06

1.01

0.96

0.92

1.48

1.44

1.34

1.27

1.41

1.61

1.51

1.46

1.47

1.43

1.37

1.87

1.84

1.82

1.77

1.94

2.16

1.48

1.43

1.43

1.36

1.33

1.84

1.83

1.76

1.71

1.87

2.09

1.38

1.35

1.29

1.82

1.78

1.70

1.64

1.80

1.99

1.41

1.36

1.74

1.67

1.70

1.77

1.48

1.42

1.63

1.57

1.60

1.70

1.42

1.58

1.54

1.56

1.63

1.76

1.80

2.33

2.25

2.15

2.02

2.18

2.40

2.21

2.10

2.03

2.14

2.46

2.05

2.03

2.26

1.99

2.14

2.32

2.28

2.48

C
sp2C
sp-C
N

1.45

O
F
Si
P
S
Cl
Br

1.89

2.67

.
- , ,
..

, ,
-- .
, ,
, ,

.. - , - . - . 2.2.

. ,
, 0.7-0.8 --,

83

84

, (, , ) ..
(. 2.3 2.4).
2.4
(. . . 2.3)

()

()

sp2-C=C-sp2

1.34

sp2-C=N

1.30

sp -C=C-sp

1.34

sp-C=N

1.21

sp-C=C-sp

1.28

CN

1.16

CC

1.20

sp -C=S

1.70

sp2-C=O

1.22

sp-C=S

.56

sp-C=O

1.16

N=N

1.25

N=O

1.17

--

. , -,
(. . 24), -
. ,
- (.. - -- )
3 5 (1,3-
, . . 24):

CH3

CH3
C CH
3
a
e H

H
a

CH3
eC
CH3
CH3

(

)

(e - ,
a - )

()
.

(,

),

-,

84

85

,
, ..
2.2.

,
,
- (, H2, N2, O2),
+-- (, HF, HCl
..). , ()

+--

,
. -
, ..
. -, -.
, , , ,
, - ,
, -
. ,
- , ,
, -
, .
.
, - ( - ),
- . , , - , ,
- ,
-, ,
-.
( -)

-)

, -
.

85

86

+
A

+
A

c
-

c
-

, ,
:
+

H3C

CH4

()

H2C

1920- ,
, , ,
1950- ( .
- 1930-
).

, .

2.2.1.

. ,

.
, , .
,
, , ,
, -, , ,
- - ,

>.

86

87

l
Cl

Cl
Cl

=2.7 ()
=2.95 (.)

=0 ()
=0 (.)

=1.57

=1.6 ()
=1.48 (.)

- - ,

. ,
,
, -l
-l . ,
,
.
, sp3-C-H ,
, (),
(109,5),
. :
, ,
(-

).

, ,

.

109,5, AlkCl
. ,
, . CH3Cl
3,86 , CH3CH2Cl - 2,00 , - CH3CH2CH2Cl - 2,04 ,

87

88

(3)2HCl - 2,15 , - CH3CH2CH2CH2Cl - 2,11

, - (3)3Cl - 2,13 . ,
.
. 1923 .
, ,
- ,
-
. ,
, .
- C-Cl
, . ,
,

, ,

. ,
- .
H H H
H C C C Cl
H H H
-

,
( ).
( , ,
.. ) .
,

.. -

.
,
.
88

89

C-Cl - ( -)
- CCl. :
H3C

Cl

H3C

CH2

Cl
CH2

CC

CCl

CCl

CH2

CCl

C2C3 C1C2
=2,04

=2,00

=1,86

Cl

H3C

,
. , 2
Cl-CH2+CH2+NH2+
, ( ). ,

(RNH2+HClRNH3+Cl-), .
,
.
.

, ,

. Cl-C
,
.

H3N

CH2

+
CH2

Cl

Cl-C)

, .

.

89

90

.
.
, ,
, .
.
()
, -
(. . 3).

2.5.

(-I), -
(+I).
2.5.

(+I)
-B(OH)2 > -CH3

(-I)
-NH2 < -OH < -F

-NH2 < NHCOCH3 < -NHCOCF3 < -N(CF3)2

( )

< NO2 < -N+(CH3)3 < -N+N

-B-(OH)3 > -COO- > B(OH)2 > CH3

-

-Se > -S > -O

-OH < -OCH3 < -OCF3

-I- < -Br- < -Cl- < -F-

-C(CH3)3 > -CH(CH3)2 > -CH2CH3 > -CH3

-CH(CF3)2 -COOC2H5 < -CN

. 2.5 ,

.
.
1.

(-),

..

, ,
,

(-),

..

. ,
( -
, - ), .

(.

1.1)

(2,20) , ,

90

91

, - . ,
, -
(N, O, P, S), , .

.
, , ,
, , .. -.
2.
, .. ,
, .
(-N+N) (-Cl+Ph, -Br+Ph, -I+Ph);
,

(-N+Me3)

(-N+(=O)O-)

. (-O-,
-COO-, B-(OH)3) (+I)-, .. .
3. ,
.
(+I)- (, -Se- > -S- > -O), a (-I)- (, -NH2 < -OH < F).
. , HgPh -SnPh3 , ,
, , ,
(Hg, Sn)
.
()

, (+I)-: 3 < CH2CH3 < CH(CH3)2 < C(CH3)3.

, ,
,
.

91

92

2.2.2.

.
,

.

, . , 6,87 :
O

(CH3)2N

-:
= 6,87

1,58 , - 4, 03
:
O

(CH3)2N

O
, 1 = 1,58

, 2 = 4,03

( ),
,
-N(CH3)2 -NO2. , ,
-N(CH3)2

-NO2 (-I),

:
O

(CH3)2N

+
2

92

93

, -
,
,
r r
r
.. = 1 + 2 . , , ,
r r r

= 1 + 2 =-1,58+4,03=2,45 .
=6,87 -

1+2. ,
.
- ,
.
.
>1+2, , 1

2 , .
( 1 2),

,
, .
, .
, .,
. . 1920- ,
,
, ,
.
(..
, )
.
- , , ..
, ,
.
.
, -

93

94

- . -
- -.

(CH3)2N

(CH3)2N

(CH3)2N

(CH3)2N

(CH3)2N

(CH3)2N

,
- - ,
4:

(CH3)2N
(. .1):
(CH3)2N

(CH3)2N

(CH3)2N

(CH3)2N

, -
():

+
Me2N

.
-
4

-,-
.
(
) , :
H3N

C Cl

H3N

94

Cl

95

(), .
2.3.8.
- -
, -.

, .. -
, -. , -,
-, , , , , ,
,

,
, ,
.

(CH3)2N

,
. , , . ,
(. 2.2.1) (H2=CH-Cl)
, .. -
( ).
:

, ? ,

, :

95

96

(CH3)2N

3,
,
.

.

- ,
.. ,
. ,

.
.

. -

.
- -,
:

O
+

96

97

+
+

. ,

, .. = 1+2 = 1,58 + 4,03 = 5,61 .
= 6,87 1,26
. ,
-
.

-
(3)2N- .
: - (, ) - (, (3)2N-)
, - - (, -NO2) ,
( - -)
, - -
- -
.

-.

, - (CH3)2N
. ,
NO2
(CH3)2N,

).

97

98

(CH3)2N

NO2
(-I)

(-I)

,
, .
.
, - (-)- .
-
- -.
. -
- ,
-.
, -
,
-.
- ,
- . ,
(4,11 ) 1--4-- ()

2,76

(6,87 ), ,
(3,62 ).
CH3
(CH3)2N
CH3

CH3

CH3

NO2

CH3
NO2

CH3

CH3

=4,11

CH3

=3,62

-
- ,
(.

98

99

2.3 2.4), -
3 (CH3)2N
NO2. - - (
) - (
),
. ,
.
,
(+-) (--). ,
(+-), ..
-
, , ; (-
), .. - .

. 2.6.
2.6.

(+-), -
-O- > -OR > -OR+2
-S- > -SR > -SR+2 (SR2 (--))
-NR2 > -OR > -SeR
-OR > -SR > -SeR
-F > -Cl > -Br > -I
(--), -
-CR=N+R2 > -CR=NR
-C=O > -CR=NR > -CR=CR2
-CN > -CCR

. 2.6
.
1.

, (+)-

99

100

(-NR2 > -OR > -SeR), (-)- (-C=O > -CR=NR > CR=CR2).
(+)- (-F > -Cl > -Br > -I ).
,

, (-).
, ,
-, -(-)-
- ( , )
, , .
2. ,
.
,

(-O- > -OR > -OR+2 -S- > -SR > -SR+2). ,
(-)-
(-CR=N+R2

> -CR=NR).

. , ,
,
(=),
.
OH

O
C

(-)-

(-)-

HCN

OH
CN
H

HCN

OH
CN
H

,
; , ..

100

101

2.2.3.

65 ( , , -CCR)
, ..
. 65 ,
- . ,
65 , - -
- .
C6H5
O

C
C6H5
(+)- 65

(-)- 65

(N, O, S .).
,

- ( -NR2, -OR, -SR, -F .),

(+)-,
,
( -CR=O, NO2, -N+N, ..), (-)-. NH-CR=O (+)- - ,
NR2
. ,
, - -
, - .
C6H5

O
NH
CH3

C6H5
NH2

C6H5

101

C
C6H5

102

.
, , ,
(+) (-)-.
,
. -
,
.

2.2.4.

. .

- ,
- ?
,
. , , , -F - (
2.1) (-) , -Cl, -Br
-I- ( ) ,
(+)- , , (+) . ,
- Cl, Br I
( 2.2) , -F-
( ), ,
(-)-. ,
(-I)-. ,
, (-I)-,
(2.1), . (2.2)
: ( 9,99) < F (9,89) < Cl (9,41) < Br
(9,37) < I (9,33), ,

102

103

- ,
. , (..
) .
X

C(CH3)2

C(CH3)2

C(CH3)2

Cl

(2.1)

OH

(2.2)

(+)-,
, . -
- , -,
(I > Br > Cl > F), , -, (F > Cl >
Br > I) , - (),
, , -(-)- .
.
(-)-, -
-, , ,
:
I

-,
. (-)-
, , (, 3)
. , (-) : I > Br > Cl (>> F).
(+)- (2.1), ,
(2.2), . , (-) (2.2)
(2.1).

. (-I)- (2.1) (

103

104

) (2.2) .
(-I)- (+)- (2.1) (-) (2.2).

.
.
(-NR2, -OR) (-I)-
(+)-. (-)-
.
.

2.2.5.

(+)-,
(. . 2.5).
(. 2.2.1),
, ..
. :
CH3 < CH3CH2 < (CH3)2CH < (CH3)3C

(. . 9).
- - .

.
,
, ,
1,3-
(. . 7).
, :

104

105

H H H
H
H CH2
H

H
H C
H

H
H C C
H

CH2

H H H

, - -

-.

-.
- - (- ), - -
- - (. .
19).
,-.
,
, ,
.

(),

()

= 0, 03 :

32

= 2,54

323
=0

= 2,54 + 0 = 2,54

322

= 2,57

= 0,03

,
(-1-),

() , 0,41 :

105

106

2=-

= 2,90

3=2
= 0,36

= 2,90 + 0,36 = 2,54

= 3,67

= 0,41

, - -=- 3
-= , - -2-2-.
.

, 2.5.4
.
(+I) (-I)-, (+)- (-)-,
, (+)- -
- (-)-,
,. ;

, , -:
F
F

2.2.6.

106

107

.
,
, , , = C=N-, (+)-, (-)-.

400 800 , .

, , ,
. ,
.
,
.
( 5) ,
, .
, . ,
, (
580 ),
, . . 2.7

,
.
2.7

, ,

400

480

530

580

610

660

720

107

108

,
.
- ,
, ,
. ,
:
HO

(CH3)2N

HO

N N

(CH3)2N

N N

-
()

( )

, . .
,
. , ..
( ).
, , , 540
, , , ,
, (480 ).
(), ()
(),
:
Me2N
max = 384
(A)

Me2N

Me2N
max = 444

max = 548

()

()
CN

CN

,
, .
108

109

Me2N

Me2N
max = 498

max = 578

()

()

CN

() =- (), () ,
() - -.
, () , () ().

-;

2.7.

-,

-.

-,

-=(CN)2

()

() , (),
() () - , ().

-, - -
,
.
=-.
, ,
, . ,
,
, , =. , -, ,
11!

109

110

CH3

CH3

CH3

CH3

CH3
-

CH3

CH3

CH3

CH3

CH3

2.2.7.

,
,
.
.

, ..
. ,
,
,
.
,
.
.

.

:
? ,

? ,
(,
),
.

, , ,

110

111

, :
,
,
. ,
, - -:
NH2

NH2

NH2
E

+E

, ,
(+)- (. . 13).
-.
, , . ,
- ,

(NO2+) , :
+

NH2

NH3
+H

NH3

NH3
+ NO2

NO2
,
. (-

I)- NH3+. ,
, ,
. ,

.
111

112

, ,
.
-
n (AlCl3, GaBr3, TiCl4 ..):
CH3O

CH3O

CH2 Cl + MXn

CH2

MXnCl

- -
,
- .
. , (+)- 3
,
:
CH3O

CH2 Cl

CH3O

CH2

MXnCl

CH2

(+)

(+)

(+)

CH3O

.
,
MXn. (+)-
- .

, - 6.

2.2.

: -
-
6

Is
() Id ().

112

113

,
.
, ..
, (
, , ).
;
, .
, ,
. , ,
, ,
,
,
(. . 25).
60
.

,
.
1965 . . .
,
(. . 25),

(., 1957).
.

2.3.1. -

2.1 ,
( )
,
() .
(), (),

113

114

.

;
,
, (
), --
.

-. -- ,
.
, . ,
56 1012
.
. ,

, ..
1 1 4 2
, , -- .
2

1'
5

5'
3

2'

3'
4

4'

1'
5'

(2.3)

2'

4'
3'

1 1 4 2
-.
(2.3) .
,
. ,
,
.
114

115

(. 2.3).
(56.56),
-- .
, 1 1 4 2

--

,
(2.3).
, ,
, ,

.

2.3.2.

(,
, , ),
-

. ,
, ,
. -

-, -
=, -NH2 ..

,
,
, , .

:

115

116

RO

+
H

CH3

CH3
C O

CH3
(R=Alk),
(R=Ar),
(R=RCO);

CH3

Me2N
+
Me2N P O
Me2N

()

()

C-O, S-O -

-
. ,
, .. ( -
- , ,
)
.
, :
R O H

H
-

-...
--
. ,

.
,
. ,
. ,
H-F.
, .
3
.

2.3.3. -

116

117

,
-- , . ,
, -
, ,
, :
CH3
+

B
CH3

CH3
CH3
CH3 B N
CH3
CH3

CH3
CH3

CH3

CH3

CH3

(2.4)

( ) , (
) , -
.

, .. - .

,
, - ,

,

. , , -
N:M, M = B, Si, .
CH2
CH3CH
O

CH2
CH2
N
CHCH3 CH2
B
O
O

CH2
CH2
O

CH2
CH2
N
CH2 CH2
Si
O
O

- ,
. , ..

117

118

, N+--.
, (..
) (N:+M-). ().
,
.
- ,
,
( ), :

()+

() -

()

()

, -
.

, ..
. -

-,

. ,
- - ,
, .. . -
-.
( ,
), -
,

- , ,
. - . 3.

2.3.4.

,

. , ,
118

119

, , , (2.4) ,

. (
(2.3)).
()
. ,
, ,
,
, - . , ,

.
,
. ,
,
,
.
,
.

. ,
(
) ()
,
, - ,
. ,
,
, ,
. -
.

.

119

120

, (2.3),
- ,
-,
- .

:

(- )

(2.3)
, , (. .
25). ,
. (2.4)

, ,
.
(. NH3; . 1.19, . 1);

(sp3 ) (

) .

2.3.5.

() ()
:

120

121

, d
.

.
d
+ -, .
.
1.

,
.
(),
:

d d, - ,
+ -,

(d -E)(a -E) = (-SE)2,

(2.5)

- (. 2.1, ),
d , S - ,
.

121

122
-

E-=

E-=
1-S

+
E+=
1+S

E+=+

. 2.1. d
() ()

. (

) d d = =
( -E) = (-SE),
, , - ,

E+ =
E =

+
1+ S

1 S

( +),
( -).

, (1+S)>(1-S), ..
,
(. 2.1, ).
,
, .. , S=0. (. 2.1, )
= ,

(2.6)

.. .
+ -
+= Cdd + Caa,
- = C*dd - C*aa,
C C* - , d a +. : Cd = C*d
= Ca = C*a = 1/ 2 . (. 1, .
1.3),

122

= 1.

123

. -

d a, (,
d<< a; . 2.2). Cd Ca

+= Cdd + Caa,
- = C*dd - C*aa
.
. Cd >>Ca C*>>Cd*. ,
,
d ; .
+ a d,
- d a. ,
+ d, - - a, .. + d, - - a.
. 2.2. , d + a -.
- =a-d
a

d
d

+
+ =d+a

. 2.2.

:
+ d + a,

(0<<1)

- - d,
- .

1
2 3.

123

124

2. ,

, ,
, , ,
.
, , ,
.
3.

( ).

( ).
, , ,
.
(2.5) +
(-) (a-d), -
(d-) (d-a) (. . 2.2).
( ,
,
).
(2.5)
(d-) (a-d) = 2 ( +)

(d-a) (-) = 2 ( -).

(+ - . 2.2), ,

()
+ - 2/.
, ,
( 3).

,
( (2.6)), .
124

125

2
. , -
,
( ).

2.3.6.

,

: 1) ; 2)

; 3) .
.

(. 2.1 2.2)
, ,
+
.
, ,
|+|<|-| (. 2.3, ). ,
2 (. 17, . 1).
, ,
, .
, ,
, ,
.
,
, ,
,
. ,
.

125

126

. 2.3.
(), - ().

,
,
- .

.

.
, ,
.. (. 2.3, ).
,
, .
2+; 2 - ,
. ,

2+=22/E,

d a, Cd Ca,
(2.7).
= 2+=2(Cd Ca )2/E

(2.8)

Cd Ca - , Cd Ca
, .
.

,
.

126

127

-qdqa/r, qd qa -
d ; r - (
1).

2.3.7.

,
, ,

,
.

(
, ),
.
, D ,
, - : ,
, . 2.4,.
(S - , - )
,
8
(. 2.4, ).
DA, ..
D ,
,
E ( (2.8)). 3D/3A
(. 2.4, ).

,
. ,
, .

127

128

- ()
( D) ()
( ; . 2.4). D
D, -
; ,
D (. 2.4, ). , D+A
D , - ,
. (, )
, (, ) .
DA
D
D

0-

(D) 3

4 3 2 1

3 ()

+ -

. 2.4, - D ; D . +

. - ,
, 0 - .

(),

D ,
= 2(Cd Ca )2/E - qdqa/r,

(2.9)

E - .

, - (
d ,

128

129

- ), ,
.. .

, , .
,

.
3.

2.4. -
,
1 (. 1.15-1.22), .
,

, ..
.
,
.

, ..
.

,
(
d-). ,
.
. .
1.15-1.22.

, -,

129

130

. 2.5.

2.4.1. -

- . ,

, .. , ( ) , -
.
-,
-.
. 1.22 (. 1),
- .

-.
, :
CH2=CH-CH2
CH2=CH-CH2

CH2=CH-CH2

1,3-

, ;
- 1,3,5-, , ..:

130

131

CH2 CH CH CH2
1,3-

CH2

CH CH CH CH2

CH2

CH CH CH CH2

CH2

CH CH CH CH2

CH2

1,3-

CH CH CH CH CH2

1,3,5-

, ,
, , . ,
, , .. .
- -,
, , .

-, -,
.
, . 2.5 (. . 2.1).
B

*=(1/(2)1/2)pA-(1/(2)1/2)pB

=(1/(2)1/2)pA+(1/(2)1/2)pB

131

132
. 2.5.
. - . 1.19 (. 1).

2- ,
,
(2.6). =+, *=*-*, ,

, * * - ,
*. , .. ,
(. . 1.3, . 1), 2+2=1 *2+*2=1.
, 2+*2=1 2+*2=1. ,

* , , = = *= *=
1/ 2 .
-

,
( *) -.
. 2.6.
1/(2)1/2
1/2

(3)

1/(2)1/2
2'

1/2

n (2)

. .

2"

1/(2)1/2

=1/2

(1)

1
1/2

1/2
1/(2)1/2

. 2.6. () () -

,
, 1, - 2.

132

133

*, , 2 , 3.
! . 2.6,

, .
. 2 2.

( 2), * (

2). , 2 2

2.

? 2

2. --
, - 2
,
2. ,

..

- -
. , -
, . 2.6, .
, -
.
- (..
-) -
- 1.
n; , - : (1),
n(2) *(3).

, (.1,) (2.8),
1/ 2 (. . 2.5) 1 ( -),

=. , 1

133

(.

2.6)

134

(1/ 2 .1)22/=1/2, ,
.
,
-
-. :

1 = 111+ 122+133 (),

2 = 211+ 222+233 (),
3 = 311+ 322+333 ().

i, -
i.
-
, - .
(=)N/2, N
,
Cij = [2/N+1]1/2sin[ij/(N+1)],

(2.10),

- i - (i=1 ); j . ,
2 -:
21 = [2/(3+1)]1/2sin[(2.1)/(3+1)] = 1/ 2 sin (/2) = 1/ 2 ,
C22 = 1/ 2 sin =0,
C23= 1/ 2 sin(3/2)= -1/ 2 .

, 2

2 = 1/ 2 1 + 02 -1/ 2 3.
, 1 3 2 ,
, , - 2 2
, .. 2.
;
, .
1 3 , (. . 2.6, ):

1 = 1/21 + 1/ 2 2 +1/23,

134

135

3 = 1/21 - 1/ 2 2 +1/23.
1 ,
, . 1

(),

( ), 2
, 3 .
-
- -
. -,
-.
, *- (. 2.7).
2

3(=)

. 2.7. -

,
(2.9), , (
):
1

= [(C1 C3 ) 2 +(C2 C3 ) 2 ] 2 / E = (
1) 2 + ( ) 2 2 / =
2
2

3
, - 2, * , ..

1 2 , 2 - 1 (. 2.7).

135

136

1 , , 4 ,
-, 2 , .
(. . 2.6 2.7).
2 3 - ,
*-
(. 2.7). , -,
- ,
,
.
(. 12).
. ,
, -

( ; . . 1).
,
, :
1

2 = 1 / 61 + 1 / 62 2 / 63

1 = 1/31 + 1/32 +1/33

3 = 1 / 21 1 / 2 2

, .
- ,
.
- :
3

136

137

1,3-

1,3-

-, . -
, : *.
.

1 2, 1 (. 2.3.4).
3 4 (.
2.8,). , ,
=CxCy (. (2.6)), Cx=Cy=1/ 2 , - -
(. . 2.5). , =1/2.
-
, 1
2.
,
(. 2.3.5).

1 3,
2 4.

(. 2.8,).
,
(. 2.8,).
. , 1
4, 1 3,

2 4.
1 3,
(.. ,
i), .

137

138

2 4,
i , , .
=(CxCy)2/E (

1
(2.8), E=2, . . 2.5) = .
8
-, ,
, -
1
- 4= .
2

4
*

4
*
3

3
2

+0.62

+1.62

1234
()

()

.2.8. ()
-. () .

,
(2.10), :
4= 0,371 -0,602 +0,603 -0,374,
3= 0,601 -0,372 -0,373 +0,604,
2= 0,601 +0,372 -0,373 -0,604,
1= 0,371 +0,602 +0,603 +0,374,

(. . 2.11):

138

139

(,

)
( )
( )
( )

,

.
- 2.4.3

2.4.2. -

-,
,
H

(CH)n

n =1, 2, 3, ... .. n - ,
, n ,
, .
,

1,n-,

, n-
, (n-2) , ..
-

-,

,
,

,
.

-.

139

140

, (
: ,
, ,
, ).
, -
- .

, ,
.

140

141

A(7)
S(6)
A(5)
S(4)
A(3)
S(2)
A(1)
S(0)

S(2)
A(1)
A(1)

S(0)
S(0)

.
. .
.

S(6)
A(5)

S(4)

A(5)
S(4)

A(3)
A(3)
S(2)

. . .

S(4)
A(3)

S(2)

A(3)
S(2)

A(1)

S(0)

A(1)
S(0)

S(2)
A(1)

S(0)
A(1)
S(0)
S(0)

. 2.9. - . (S) ()
. .

141

142

.
, .
.
.
.

,

. ,
-
.

2 ,
, .
( ) .
,
, (2.10).
. 2.9. -
n=1-8, 1, 2 3,

, .
,

.

2.4.3.

, , ,
,
.
,
. .
142

143

,
.
, , ..

.

. , -
, , - (. 2.9).
,
(+) (-)
.
, ,

:
-

2(-)

2(+)

(.
. 2.7), ,
,
. , (.
. 12) 6(+),

2(+),

2(-)
6(-).
,

,
().

,
()
143

144

,
.
:

*

*
*

*
*

(, ,

*
*

*
*

*
*

2.4.3..

- -
(. . 2.8)
- . ,

.

,
.
(-) (+), -
-.

144

145

- .
() ,
, ..
(. 2.9).

, .
, ..
,
(.

2.7).

-. -

, 1 2.
*-. ,
: (2) (+).
.

2.4.3..

,
.
.
4 ( 2.4.2),

(, 1 4 2 3
) ,
-. ,

=0,5,

, - (

145

146

) (2 C 2 =1). , (,
, , , ..) -

.
.

(n). Cn
, -, .
:
1) ,
;
2)
(. ; . . 2.6);
3) ,
, ;
4)

=1 ( ).

,
( , ):
*

1) ,
;

2)
0

0
7 2

3)

. ,
4,
2=-, 3
.

146

6
5

1
4

2
3

147

. ,

,
(, y, z ..),
,

:
2/ 7
-1/ 7

-1/ 7

1/ 7

4)

2
n

=72, = 1/ 7 .

,
n = (1 / 7 )( 2 + 4 6 + 27 )

(.
2.10) ( ) -

( ) +

) + 2(n) = 1. (
):

( ) = C 2 (

). 2 C 2 ( ) + 2(n) =1.

147

148

2
6--

7--

2
8--

.2.10. - .

, ,
n, .. n (. 2.10).
,
,
n2 . , , n

:
-4/7

+4/7

-1/7

+1/7

-1/7

-1/7

+1/7

+1/7

(-)- -2+ (+)- -2-.

(. . 2.8) ,
- .
.
.

148

149

.
() , , ..
,
. ,
-,
.
, . (
) , (1,48
1,54 ). .

, ,
, .

,
.
,
- (91 82 / ). ,

, .
-.
,
, 1,4:
CH2 CH CH CH2

+ Br2

CH2 CH CH CH2
Br

Br

CH2 CH CH CH2
Br

Br

, . 2.8 2.9 ,

, , ,
. , ,
.. (

149

150

) ,
(. . 7).
, -
. , ,
- .
, -.
- , , ,
sp3-:
H
H

H
C

sp3

H
H

-,
. , 1,5-,
, :
CH2 CH CH2

CH2 CH CH2 2 2
1,5-

- -,

:

CH2 CH CH2

CH2=CHCH=CHCH=CH2
1,3,5-

,
-. ,
,
,
: -
?

150

151

n-,
(. 2.11).

- (
, ),

. 2.11.

(.

2.8,),

:
= 2 = 2CxCy,

(2.11)

Cx Cy - y n
.

-
- .
,

(2.11)

xy xy:
1/ 2 x
1/ 2 y

x'
y'

-1/ 2
-1/ 2

E=2(CxCy+Cx'Cy')=2

1,3,5-
E=2CxCy=

, , .. ,
, -, = -.
, (. . 12).

151

152

- (
),
:
1/ 2 x
y. 1

x'

-1/ 2

E=2CxCy= 2

E=2(CxCy+Cx'Cy')=0

, CxCy CxCy
. ;
, .. ,
.

(=0), n- ,
. -
, , , ,
. , ,
(. 2.12), (.2.7).

22=4, (. . 2.8)
(21,62+20,62)=4,48, .. 0,48 (,
<0).

152

153
2

4
4

4=

1
1
1
1
1- 2+ 3- 4
2
2
2
2

3=

1
1
1
1
1- 2- 3- 4
2
2
2
2

2=

1
1
1
1
1+ 2- 3- 4
2
2
2
2

1=

1
1
1
1
1+ 2+ 3+ 4
2
2
2
2

. 2.12. - .
( =1/2).

. ,
:
1/ 2
x
1/ 2
y

-1/

E=2CxCy+0=

E :

.1 y

E=2CxCy=

, ,
.
, , ..
, ,
. :

153

154

1/ 5

-1/ 5

1/ 5

1/ 5

.1

-1/ 5 1/ 5

.1

E=2/ 5

1/ 5

E=3(2/ 5 )=6 5

1/ 5
1/ 5

1/ 5

.1

E=2(2/ 5 )=4 5

2.4.4. -,

, 2 ( ) . ,
- ,
, , 2=2 2=,
2=-2- - - 2=- 2=-=2 - 2=-=,
- , 2-
. ( ,
, ), >=
(. 2.13).

(. .
2.5.3).
.
(1/ 2 , . 2.5), Cc<Co, a C*>Co*, Cc/Co= C*/ Co*.
,
, -

154

155

C O

()
+=Ccc+Coo (Cc<Co)
=Cc*c-Co*o (Cc*>Co*)
Cc/Co=Cc*/Co*

c
C

o
+()

2=2,

2+=O

,
*

C O

,
. 2.13.

-
. + -

.

,
.
, ( ).
.
.
(, +) :
C O +H

C OH

C2 C1 O

*cc
c

cc

2
o

. 2.14. - - .

155

156

- - (. 2.14) -

(. . 2.6). - 1

(. 2.13); , ,
,
*, 2. 2,

*, 2 , *.
:
C2 C 1 O

C2 C1 O

+ C2 C 1 O

C2 C 1 O

, 1 2
* ( ). 1
2, -
*. , *

1 2, 1 . * 1
, 2 , 1,
* 2 ,

1 - -.
2 3 :
C2 C 1 O

- C 2 C1 O + C2 C 1 O

C 2 C1 O

*cc
2
2

cc

C2 C 1 O

C 2 C1 O

C 2 C1 O

C 2 C1 O

3

2 , .
1 2 , 1 - . 2
( 2
), 1 ,
(. 2.14),

156

157

1 . ,
, 2 (. 17).
, 2
2, . ,
2 (
2; . . 2.14), ,
, ,
2, - (. . 2.3.7),
,
, - , , ,
1
(. . 2.14) -
3 1, 1
. -
- , , ..
.
, ,
, 1 2 .
,
- . 2.14.
(. 2.7).
2.7
-

, ( ) ( )
, ,
,
, (
) , .
,
157

158

(. 1.3, . 1),

.
- - ,
(. . 2.6 2.14): ,
, - . : , 2
, - 1 .

, (. 17), ,
,
.
()

2=-

. 2.15.

,

. 2.15. - .
2

, ,

2, 40

/ 2. -

. 2.8. -

3, -
2,
.

- ,
,
.

158

159

.
, 1 ( ),
;
. 2
, 3
, , , 3
( , ).

..

. 2.15. 2.
(1) (2), ..
. ,
-
(. . 2.5) -
(. . 2.13). -
, - - ,
. , , 2
(3) (2) , (1) - ,
- (. 2.15). , (,
) :
,
, .
4
*- -
, , ,
*- (. . 2.6). ,
(. 2.13). *-
(2), *- =
, . (3) (1)
, (2) - , - .
1 ,
-= -=.
(. . 2.8). (1)

159

160

, .
- . (2)
(3).
: : (1) (2)? ,
(1), -
- - 2- ,
1-
, (. 2.14).
, , . 2.15.
1 : (3) - , (2) - , (1) -
- .
, 3,
, *-= *-=,
(. 2.8), , ,
: (3) - , (2) - ,
(1) - .

, , . 2.7 (. 2.8).
2.8

,
,
. ,

, , -,
.

160

161

2.4.5.

FCH=CH2 -, - .
(+=-0,07)
- (2). ,

-
, - -
:
F C1 C2

F CH CH2

(
)

F C1 C2

F C1 C2

- F (2)
, (1), -
7, -
- -F, (..
):
F

CH
+

CH2
+

- cc()
cF()

,
-
- .

7

- -. - , - - .
161

162

- .
(. . 5).
- , , -,
-.

2.5. -

2.5.1. -

-
.
-, -.
-, -
.
HF (. . 1.9, . 1).

2.5.1.. HF

HF H1s
(2s, 2p)
. H-F 2s
2p- , 2py- 2pz-
1s - (. . 1, . 1.7).
z

F2 p x
F2 s H1 s
H1 s
,
y
-

162

163

, H-F
: H1s, F2s F2p.
()
(), H-F :

*. ,

(. 2.4.1) -
.
H

H-F

4
3

1s O

pz
py
px

*(HF)

3
2

n
n

(HF)

O 2s

. 2.16. HF.

H-F . 2.16.

, 1s-
. 1 F2s, F2s.
2s- 1s-
2- :

+
F2s

H1s

H-F

.
F2px

HF

1 HF,
,
.

163

164

s-

s - - (. . 1, . 1.7). ,
F2s-H1s.
F2
( ) ,
1 F2s H1s. 1 F2s, H1s,
, F2s, H1s
( H1s ). ,
1 , ,
, (.
. 1.17):

H1s

F2s

, ,
5 :
, :

H1s

H-F

F2px

HF

F2s

HF (. 2.16). -
2y- 2z-,
. 2 - ,
1s - 2s :

+
F2px

H-F

n(HF)

F2s

H1s

F2px
H1s, 2 :
+

n(HF)

, 2 ,
H F (. . 1.17, . 1),
164

165

2 (n). , HF
n- n-. n ,
n ,
F . nn-
n (. . 1.17).
, (HCl, HLi, HO, HC, HN, HB
..), - ,
.
, ( ),
(. . 27), ,
HF, n :

.
.

H-C
()
(n)

()

C2s 2
,
sp- (. 1, . 1.8). n

.
n.
,
, ..
. (.
2.17).

165

166

C-H

*CH

H1s

Csp3

CH

. 2.17.
.

sp3-
s- . sp3 H1s, *,

. ,
1 5.

:
*HX

*HX (5)

n (3, 4)

nsp3

n (2)

HX (1)

HX

sp3
n ( , ,
), py pz
, sp3-. - . HF
: H-F

166

167

sp3-
:
H

2.5.1..

(.. ) -

, 3
33, 3 - (3)
..
.

4.
,
(, ) 2,

:
H '

H
H

H
H

H
4
,
, , 1s-,
, ..:
s2'

s2'
s2

s2

s1

s1

s'1

167

s'1

168

4?
,
1s- ,
. (. 2.3.4 2.3.5)
- 2,
( ,
), 4
1 2:
H2 s2'

s2 H '
2

s1

s2 H2'

s1

H1'

'
H1

H1'

s2'
s2

1=+'
s1

s'1
s2'

H2

s2'
s2

2='

'
H1

s'1

s1

s'1

1 , 2, 1
s- ,
, 2

, ,

.
-, *-
,
. *
,

*,

, ,
,
. , 4
- 3 4 - :
4='*

3=

168

169

3 ,
H1 H2, 4 -
, 1 2.
. 2.18.
4

'*

'

. 2.18. 4

2, 3 4 (
),
( ). , , ,
* * . ,
, 2:

+
-

, . 2.18, ,
4
1, - 2, 3 4.

, ..
.

4, .. .
1s- ,
,
169

170

.
, 1,
4, , , 3 4 .
4 ,
1s- .
4 4,
1s-,
:
1s

,
, .

.

,
.

2.5.1..

, . . 2.19

4.

170

171

H
H

H
H
H C
H

H
H

5
5

px
py
pz

4
3
4
3
2

1
. 2.19. .

,
. ,
2s ( )
1 ( ),
,
, 4
,
, :

. 2.19
,
.
-

171

172

(1), , - (2,
3 4), *- (5)

, *- (6, 7 8).
, . 1.15
(. 1).
. 2.19
( ) .

, sp3 (. 1.8, . 1)
1s- .
- ()
(*):
*CH

Csp3

H1s

CH

sp3-
.
:

, ,
(. . 1, . 1.9).

(.

.2.19).

sp3-

172

173

Td.
,
4 (. 2.20).
8

6 7 8
6

7
5

4
3
2

1
1

. 2.20.

, ,
4 .
,
pz,
6, 8 . 4,
(.. ) d, d - ( )
4:
+
4

dx2-y2

, , CH4,
SiH4, GeH4, SnH4, TiH4
, d-
( ) 4.
173

174

d-

.

. ,
, .. 4.
4,
.
SiH4, d-
.
1 (. 2.20) ,
2, 3 4, , , ,
.

2.5.2.

, ,

. ,
3, 2, -
. 3
4:
H
H
H

H
H

3,
(C3v) :

( )

( )

174

( )

175

, 2s- 2-
, 3,
3 (. 2.21).

2, 3 4.
z
x
6

7
6
5
pz
py
px

3
2
1

3
2

1
1

.2.21. CH3.

C2s-, pz-
. , 1
3
pz-,
1 pz .
, 4
1 pz :
4

175

176

1 s (. 2.21)
. , 1-pz
. , 4,
1, s pz, ,
, .

, 1s- ).
1, s pz
:

. ,

, -.
3 s-
, 1
(- ) pz:
+
1

C2s

1 s, 1 pz. ,
, pz, 1 s 1 -:
+

+
1

C2s

C2pz

C2s

5 :
+

C2pz

, :

176

177

C2pz

1 5,
, .
5 1
3 .
.
(2 3) (6 7)
3 ,

2 2 6,
3 3 7.

2.5.2..

26
3.
. . 2.22
3,
(
). 14 ,
, (8)
, .. . ,

3 - - (*).
6
7, (2-2) (3-3).

177

178

z
8

8
4

6
3

3
5

2
1

. 2.22.
3

- -. ,
4 ,
2 3. 4,

.
5, 6 7.
1 2
-.
3, 4 5,
, 1 2. , -

178

179

-.
. , - (98
/) 16 / - (82 /).
2.5.2..

2,
.
2,

4:
H
H

H
H

-2

H
H

: 1
2:
1

2
. 2.23.

179

180
z
x
6

5
6

pz
py
px

3
2
1

s
1
1
. 2.23.

2.

1, 2, 5 6
:
+

1
2

+
py

py

px

pz ,
1, 2, , 2
pz -.

180

181

3 2
1, s
3 (. . 2.22) -
(. . 2.6):
-

+
s

px

, ,
,
3.
,
2, . 2.24
( 2).
8
8
7

4
3

5
5

3
4
2
1

. 2.24. 2.

12 ,
6, - 7. ,

181

182

(. 2.22), 2
7,

-. 6
7 . 4 -,

, ,
. ,
,
6 7 .

2.5.2..

,
:

4 (C2pz)
3 (C2px)

. 2.25.

182

183
8
7

4
3
2

4
3
2

5
5

4
3

1
1

. 2.25.

2 + 2 2=2
,
, . 2.24. :
.

:2

.
s-, 3, 4. . 2.24, :2
3-3 4-4 :
4

, 3 3, .

, (3) :2
(4) :
H H

H
H

183

184

, :
HH

H
H

H
H

22- 22+
, . 2.24, ,
:
H
H

H
H

H
H

H
H

, , . 2.23, 2.24 2.25,

.
, ,
, ,
,
.

2.5.3.

, (,

CLi4)

, , .

.
.
, , , ?
?
4, - IV ,
?

184

185

4.
D4h ().
1s-,
. 4 (. . 2.18),
4 , ,
*-
2 (. 2.26).
4

3
2

. 2.26. 4

, -;
4
, 2 3
. 2.26.
3 4
90.
,

, :

185

186

+-

, 2
2.
.

5 ()

4 ()

3
2
1

pz
py
px

3
2

3
2

1
. 2.27.

. 2.27.
. . 4
.
-:
. .
1, 2 3 ( 2 3 ).
- 4
(z), . ,
(4) . (5) 4. .
(3d-

186

187

) , 4
.
,
141 / (, 1985),
- (104 /).
,
, . ,

, ,
:
a

c
d

c
d

a
b

a
b

(-)-

(+)-

4 3-,
- , ,
- -:

H
H
H

+ H

, ,
.
,
- (-) - (+I) .

- .
, (-) (+I)-.
. ,
-
5 / ( ). - 17 /
187

188

, -. , -
2- (. . 12),
:
Li
H C
H

Li

Li

-
()

Li

, ,
4 .
,
z,
6, 8 . 4,
(.. ) d, d- ( )
4.

+
4

dx2-y2

, , 4,
SiH4, GeH4, SnH4, TiH4
, 3d-
( ) 4.
TiH4 d-

.

. ,
, .. 4.
4,

188

189

.
SiH4, d-
,
, . SiH4
4, - pz, ,
, pz, - 4.
,
IVa, .. , , ,
IV, .. , , -
.

2.5.4. ,-

.
(. 2.2.5).
32+. ,
,
- - :
H
H C CH2
H
, ,
3, 4 5 , 1 - ,
2 - (. 2.28,).

189

190

H4
H1
H3

C2p

H5

H2
H1

H3

H1

C
2

H2

H3

H2

H1
H3

C
H2

H1
H3

H4

C2p

H5

H2

. 2.28. : -
; - () -
-; -
- - .

,
. ,
2 * 3-.
1- 2-,
.
,

1-

2-

.
. 2.28,.
1 2
+ -. + -

.
-. -, 3

190

191

2-,

- () - 2 () .
-, - 2 :
.
- -: -,
109,590=19,5 (. 2.28). , 2
- ,
(-+2),
, -.
"" ,

2.28,,

. , ,
, ,
32+ , 3+.

2.6. " " "

"

. ,
,

.

,
,
.

191

192

" ", -.
.

2.6.1. -

2.6.1..

(" "),
, - ( ), ,
, n- n-,
-:

..

H H

H
H

.. . .

H
H

n- n -.
,

, . 2.29.
(. 2.29,) ,
-, - *; - *-.

192

193

6
5
5

4
n

4
3
2
3

n
1

2
1

4
4

6
5
4

3
2

. 2.29. n- n-
(); ()
( ).

, 5 6 ,
2 3. , ,
:
+

193

194

-, - ""
(. 24). - (. 2.29,) --
, 1, 2 3
. 2 3 , -,
, . -
, . -

--. , 2 3, ,

. 4 ()

--

, 2/3 . 2
3 - . , (), (), (14 / ). - 3:

CH3
+
CH3
(A)

()

194

CH3 CH

1
3 2

195

(1)-(2)
(1)-(3) (2)-(3) ,
(CR2, -CN, -COOR),
(1)-(2) (1)-(3) (2)(3). :
OH

1,53 A

C O

1,46 A

C O

O
, ,

R:
R

. R=H,
, R=CN,
.
2 ( )
" ":

,
25+,
.

195

196

[3.1.0]
, .
, C3v.
, 1/3

1/3.
, 3:
+

OTs

-TsO-

2.6.1..

.
.
.. ..
..
, ,
, . n n-,
, . 2.30.
(3 4) (5 6).
3 4 , 5 6 - ,
,
("
").
(--*-*)
2 7 .

196

197

8
8
7

6
5

n
4
3
2

3
2

. 2.30. n- n-
() ()

, . 2.30,
, . , 3/6 4/5
:
+
3

3 '

6'

+
4

4 '

5'

, 3'/4' 5'/6' ,
3", 4", 5" 6",

197

198

*-
:
+3 '

3 ''

4 '

4 ''

+6'

5'

5''

6''

, , . 2.30

, . ()

() .

.
.

()

()
, ,

1,3-

, -
.
, :

198

199

. .
()

()

. 2.31.

()

()

* A

3
2
3,4
S

S
1

. 2.31. 2,3--[2.2.1]

,
,
. - 3 ( 4)
, , , , *,
, 7.

.
( ).
2 7- , ,
, 3* (. 2.32).
, ,
(. . 2.8).

199

200

,
( - ). . 2.31,

(3)

. ,
,
,
, ,
.
,
-. ,
, .

4
3

S
A

3,4
S

. 2.32. [2.2.1]-2

2.6.2. " "

, " "
.
, , ,

. , " "
, .

200

201

, .
,
.
1,4[2.2.2], .
" "
n+ n-, :
N

1,4-[2.2.2]

n-

n+

, ,
n+ n- . ,
. ,
, n+ n-,
2 (7,52 9,65 ).
, n+
n-.
,

. *-

-, (. 2.33).
" ". n+ n *- -. 1,4

"

"

1,2-

(n+ n- *) .
* n+ , n- . ,
.

201

202

n+'
nn-'

n+

n+'
.

2.33.

n-'

"

" 1,4-

[2.2.2]

,
n+ 1,72 , n- :
N

" " "

" .
-3,7-, -, :

()

()

- - "
"

,
- (IP=0,97 ) , - (IP=0,36 ).

, - , ,
, -,

202

203

5"
+'

+'

"4

'

'

(a)

5''
+'

+'
-'

-'

4''

. 2.34. - () - () -3,7

. " ".
. 2.34,, " " -
, + -. + -

4"(3")

5"(6")

. " " (+ -4") (- -5")

+ - . -

"

"

+ - (. 2.34,), ,
-, + - . "

" .
1,2- -
203

204

- . , +

- -
+ -, .
, " " -
IP - ,
.
" " , , , .. -.
, , ,
1,2- .
, " "

.
-:

204

205

3.1................................................................................................................................... 206
3.2. .............................................................................. 209

3.2.1. ....................................................................... 211

3.2.2. .......................................................................................... 213
3.2.3. ............................................................ 215
3.3. ........................................................................ 220

3.3.1. ................................................................................................. 220

3.3.2. ................................................................................... 222
3.3.3. - ...................................... 233
3.3.3.. .................................................................. 233
3.3.3.. - ....................... 236
3.3.3.. ............................ 238
3.3.4. ....................................................................................................... 246
3.3.5. ................................................................... 253
3.3.6. - ........................................................................................... 260
3.3.6.. ............................................................................................ 261
3.3.6.. ..................................................... 263
3.3.6.. ........................................................... 265
3.3.7. ......................................................................................................... 269
3.3.7. ............................................................. 270
3.3.7. ()<0 ()>1 ............................................. 273
3.3.7.. ..................................................................................... 275
3.3.7.. ...................................... 275
3.3.7.. ................................................. 277
3.4. ....................................................................................................... 280

3.4.1. - ..................................................................................... 280

3.4.2. .................................................................................................................. 284
3.4.3. . - ................................. 285
3.4.4. ................................................................................................................ 287
3.4.5. 289
3.5. - ....................................................................................... 292

3.5.1 ............................................................................................... 295

3.5.2. ................................................................................... 299
3.5.3. .................................................................. 301
3.5.3.. ................................................................ 301
3.5.3.. s- ..................................................................................................... 303
3.5.3.. .................................................................................................. 305
3.5.3.. .................................................................................................................. 306
3.5.3.3.. ................................................................................................. 307
3.5.3.. , ........................................................................... 311
3.5.3.. .................................. 313
3.5.3.. ...................................................... 313

205

206

3.1.
, ,
() .
.
, :

:
+ -
+ - .
, :
+ + .
(

- ,
. 2.3.2 (. 2) , -
, , ,
.
: ,
, , , ,
.

300 . XVII . .
, - , (
), - , ( ),
, . XVIII .
" " ,
( "", S
uerstoff ..). , 15 , ,
HCl . XIX XX .
, -

206

207
- , ,
NH3 , - NH4+.
1920-
, . 1960 ,
"" "" .
; , "" ""
.
- ( ),
. , ( )
() .
( ), ,
.
, (6 8).
- :

(C2H5)2O +

F-

(C2H5)2O+- -BF3

BF3

SbF5

AlCl3

SbF6N+ AlCl3

(CH3)3N

Br-

(CH2)3N+-B-(CH3)3

B(CH3)3

CH3Hg+

CH3HgBr

, , - .

, ,
:

207

208

(H3)3OH

(CH3)3C+

OH-

(CH3)3CO-

H+

(CH3)3COH

CH3COO-

CH3-

CO2

(CH3)2S+--BH3-

BH3

(CH3)2SH

(CH3)2S

2CH3+

S2-

.
, , ,
,
. ,
:

(CH3)3C

(CH3)3C+ + Cl-

Cl

O-

O
Br

"Br+" +
-

2-

, ,
.
, (, t-Bu+),
(ZnCl2, AlCl3 ..), (RMgX, R4Sn), (BF3,
BH3, R3B) ..

, , ,
. , , ,
, .. - .
, .
.
, ,

(, ).

208

209

(, , ..), ,
, ,
, .
.
,
, ;
:

- + +

(3.1)

-, +, -
, + - .

, ,
. ,
(O, N, S ) -, NH-, SH-, - ..
,
:

H3COOH +

(-)

H3O

CH3O

CH3COO

H2O

CH3NO2

C6H5O

(-)

H2O

CH3NH2

H2SO4

CH3OH

-
+

CH3NH3

(NH-)

HSO4

CH2=NOO

H3O

C6H5OH

(-)

, ,

(3- 3-; CH3NH2 2; 2 HSO4-; C6H5O- CH2NO2-)
. ,
.

3.2.

209

210

:
K

+-B

AB
A B

(3.2)

- .

, . ,
,
.
,
. , BF3 - (-),
. -
- -, -.
(NO2+) N- ..

BF3

(CH3)3C+

NO2+

N-

H3NO2

CH3NH3+

N-

CH3O+
-
CH3OH
-

, (3.2), ,
. ,
(. 2.3.4, . 2),
. ,
- () ,
BF3 - .. , , ,
, -; (3.2)
, , ,
, . ,
3+, 65+, (65)3+, 3-+= ..
, ( )
- (, CN-), N- -.
-, ..
, -, .. . ,

.

210

211

3.2.1.
( )
( ) . ,
,
.
, .
( ; . . 3.3),
,
, , , .
.
,
. , F , -
Hg2+ Pt2+. (R3P), (R2S)
(I-, Br-) :
( RSH - "" corpus mercurium captans", .. ", ").
, Hg2+ Mg2+, 2,
, R2S.
,
, - XIX
, , Al, Mg Ca,
, , Cu, Pb, Hg,
.
1963 .
( ),
.
1954 . ,
:
logK/K0=aP+bH
K - ( (3.2)); Ko 2 ; P - ; H
- () , ..
+, 3+ ;
a b - , .
, ,

211

212
, H, ,

P.
,
( ).
,
(H>P). (S2-, Et3P)
, (. . 2.1.2, . 2):
, , (
), , .
(OH-, F-)
.

, .
, , .
,
(, H+, Li+, Mg2+, BF3), ; ,
: ,
, ,
. ,
, ( d-)
..., , , .
:
;

.
,
. ,
, .
( );
S2-, , , ( ),
( ).
( ) V-VIII ,
.
, :
I-<Br-<Cl-<F :
NH2-<OH-<F , :

212

213
Li+>Na+>K+
Zn2+>Cd2+>Hg2+
. 3.1
3.1
,

H+, Li+, Na+, K+, Mg2+, Ca2+, Al3+, Cr3+,

H2O, OH-, F-, Cl-, RCOO-, PO43-, SO42-,

Fe3+, BF3, Me3Al, AlCl3, SO3, RCO+, CO2

ClO4-, NO3-, ROH, R2O, RO-, NH3, RNH2,

N2H4

Fe2+, Cu2+, Zn2+, SO2, R3C+, BR3, NO+

PhNH2, N3-, Br-, SO32-,

RHal, ROTs, CH3+, RCH2+, Cu+, Ag+, Hg2+,

RSH, R2S, RS-, HS-, S2-, I-, SCN-, CN-, S2O3-

CH3Hg+, BH3, , (0)

, R3P
CH2=CH2, , R-, H-

3.2.2.
. , . 3.1

.
3+ () I- (). "",
,
, "-" "-".
K

H3-OH + H-I
-

K=

H 2O CH 3I
HI CH 3OH

CH3I + H-OH
-

, : K109 25 .

(3+=, ) RS- -,
"" :

213

214

O
CH3

+ RO-

SR

+ RS- OR

CH3

, ,
.
,
. ,
, -,
(. 17):

O
C

+ R-X
CH

O R

-X-

+
CH R

CH

, , ,- ,
(. 16):

O
Y +

+ YR

R
- O

- , ,
, " "
R-X (.. R+) .
Y-, - - ,
.
- =- ( ; . . 16).
.

,
. "".
, ,
. , [Co(NH3)5F]2+ ,
[Co(NH3)5I]2+, NH3 ,
, . ,
CN-, : [Co(CN)5I]3- ,
[Co(CN)5F]3- .

214

215

3.2.3.
,
" ".
"",
" ".
,
.
.

.
. 3.1. (G) -
:
G=-[()-()]/2.
()
:
= -[()+()]/2.
G, "". ,
.

GB

GC

GA
B
()

()

()

. 3.1. .
. ,
,
.
( (3.2)). , , ..
- ,

215

216

. (N )
:
N=(A-B)/GA+GB).

(3.3).

, N ,
, ,
.

,
, ..
.
,
:
1) ,
;
2)

, ,

;
3) .
,
.
(3.3),
G , - (
, ).
.
:
, ,
.
. (

) ( )
, ,

(. 2.3.6) () ().
-
.
: -,
, -
.
. 3.2
() .
, ,

216

217
,
. ,

(
"-"). () () , ..
.
s- (Cu+, Ag+, Hg2+) (Br2, I2,
(CN)2C=C(CN)2), - CN-, RS-, R3P,
() .. (.. . 3.1).

. 3.2.
- ( , )
. 3.2 "-".
() () ,
.
,
, - ,
(. ).
( +, 2+, Li3+ ..)
, (
), , . ,
, ,
, ,
, , , .
"" ""
, (. . 3.1).
() (), () (), ,
, , -

217

218
. , () () ,
() (), , .

,
, " () ".
, ,
, .. ()
(. 27)
(. 25).
. "-"

.

(. . 2.3.5, . 2).
. -
, , ,
(. 2.3.5, . 2).
"-" (. . 3.2),
.
, (OH-, F-, NH3, RNH2 ..)
(H+, Li+, Na+, BF3, AlCl3 ..).
"-" :
-.
"-"? (3.3) , GA GB "", , , "-".

.
; ,
. -
.

, . ,
, .
, ,
" " . ,

.

218

219

+ -

+ -

+
-

. 3.3. ( )
- . ""

. 3.3
- .
,
, .
, (- )

. , , 1/R, R , ,
, ,
, .
.

. Li+ - , ,
. Li+
, 2s- ,
.
(OH-, F-) ,
, ,
. , Li+, OH-, F- ,
.

(; . . 3.2.2).
"" (, ,
)
. "" (
) . ,
"". ,
- ,
,
.
Li+ ,
- (. . 11) . ,

219

220
, Li+ , ,
.

N
O

O
,

Li+
[2,1,1]-

Li (OH2)n

Li
O
O

3.3.

3.3.1.

"" .
" " " " ,
" " -, " "
.
,
"" "". (3.1)
, , - , -,
+ . ,
.. . ,
. , ,
, :

+ 2
+ 2

- + 3+

(3.4)

+ + -

(3.5)

220

221

HCl

HCl
NaOH (
)

, ,
1 . 3.4.
.

3.4.

(1)

(2)

(
).

, .

, HCl
.
(HCl
NaCl), .
-
N.
(. 3.4, 2).

,
(3.4). .
(3.6), ,
, - (3.7):
3+ + - 22

(3.6)

3 + - 3- + 2

(3.7)

(HCl)

( 3+, 52+, 94+ ..),

221

222
(3) - 3+, .

- ( (3.5)), -
-, .
, , (. . 3.3.6).

3.3.2.
,
, , , ,
.
:

3+ + -

22

(3.8)

(3.8)

=
0

a
X

(
)2
2

(3.9)

= aX/aX0 - ;
0

, .
(3.8) ,
( 2 1 ),

.
, (3.8) ,
3+ - .
3+ - (
1
/).

0 =[H3O+][OH-],
[H3O+] [OH-] - ; - ,
1,00.10-14 2/2 25.
(3.8) , [H3O+] = [OH-],
14
= 10-7 25.
[H3O+] = [OH-] = 10

222

223

, :
= -lg[H3O+]
= 7,00, [H3O+]>[OH-] <7,
[H3O+]<[OH-] >7.
[H3O+] [OH-] ,
, .

( = -lg[] ) 25.

2H2SO4 = H3SO4+ + HSO4-

2,9
-

2HCOOH = HCOOH2 + HCOO

6,2

2HF = H2F+ + F-

10,7 (0oC)

2CH3OH = CH3OH2+ + CH3O-

16,7

2FSO3H = FSO3H2+ + FSO3+

17,4

2CH3CN = CH3CNH + CH2=C=N

+

19,5

2NH3 = NH4 + NH2

27,7 (-50oC)

:
AH + H2O = A- + H3O+

(3.10)

(. (3.9):

+
3
=
2
0

0 0
2

0 0 ,

(3.11)

0
- (=-, 3+, , 2)

( 2 / 2 )
( )
.
0

():

+
3

( ) =

0 0

(3.12)

,
1 / 25. , (3.12)
0

, . ,

223

224
, ,
.

(),
() =

H 3O +
H

(3.13)

( 25). , ()
, , , ,
0

()
.
(), ( (3.10))
.
() :
() = -lg().

(3.14)

, , .
(3.12), (3.13) (3.14)
() = - lg

(3.15)

,
.
(3.13)
=

H 3O +
H 2

1014
=
.
55, 5
2

, (2) = 15,7 25.

. (3+) = - pKa = 14-15,7
= -1,7.

- ,
, . , ,
, , [A-],
[AH].
(. 3.3.4). . 3.2 . <0
>20 .

224

225

() ( (3.12)).

+ + -

+ 2

, ,
.
=

.
,
+:

+ + 2
(+)=

+ 3 +

3 +

, - + + , -
.
+ - ;
. -
+,
. +,
-, - ,
+ . . 3.3 .
, (+).
,
(+) -2 17 .

225

226

3.2

HI

-10

HBr

-9

HCl

-7

H2SO4

-3

HNO3

-1,4

NH2SO3H

0,99

HSO4-

H2S

7,0
-

H2PO4

7,20

HCN

9,21

B(OH)3

9,24

H2O2

11,7

HPO42-

12,4

2,0

HS-

14,0

H3PO4

2,15

H2O

15,7

HF

3,18

OH-

21

HNO2

3,3

NH3

33

H2CO3

3,88

CH2(CN)2

11,2

NC

-11

NC

NC

CN

CN

226

227

-5

HC(CN)3

()

2,4,6**

NO 2
O2 N

12,2

NH 2
NO 2

CH3SO3H

HC(NO2)3

**

CF3COOH

0,23

2,4-**

F3CH2OH

12,4

(CH3)2C=NOH

12,4

()

NO 2
O2 N

CCl3COOH

0,66

15,0

NH 2

CH3CONH2

15,1

0,71

CH3OH

15,5

CHCl2COOH

1,26

CH3CH2OH

15,9

CNCH2COOH

2,47

2,4,6-
( )

NO 2
O2 N

OH
NO 2

16,0
H

CH2ClCOOH

2,86

(CH3)2CHOH

17,0

HCOOH

3,75

(CH3)3COH

18,0

227

228

2,4-

NO 2
O2 N

4,09

18,4

4-
O2 N

NH 2

OH

C6H5COOH

4,20

**

C6H5COCH3

19

CH3COOH

4,76

CH3COCH3

20

(CH3)3COOH

5,03

C6H5CCH

21

C6H5SH

6,5

**

CH3COOC2H5

24

7,15

CH3CN

25

7,23

HCCH

26

8,36

**

C6H5NH2

27

4-
O2 N

OH

2-

NO 2
OH

3-

O2N
OH

**

CH3COCH2COCH3

**

(C6H5)3CH

31,5

(CF3)2CHOH

9,3

CH3SOCH3

33

C6H5OH

10,0

**

C6H5CH3

41

CH3NO2

10,2

C6H6

43

C2H6SH

10,6

CH4

50

(CH2)6

55

-2-

228

229

65

***
H H

OH + H2O

O2 + H3O

** ;
***
33-

3.3
+

( ) ( ) 25

()

()

NH2NH2

8,0

NH2
2-

33

21

HS

7,0

OH-

15,7

NH2OH

6,0

H2O

-1,74

2-

14,0

NH3

9,25

229

230

1,8-()2,7-

1,8-

NEt2

16,3

NEt2

CH 3O

0,8

OCH 3

NH=C(NH2)2

13,6

NH=C(CH3)NH2

12,4

NEt2

NEt2

CH3CONHC6H5

0,4

NH2CONH2

0,2

12,1

CH3CONH2

11,15

2-

()

NH2

-0,25

NO2

(C2H5)2NH

10,8

(CH3)2NH

10,7

(C3H5)3N

10,7

CH3NH2

10,66

C2H5NH2

10,65

1,4-

-1,7

CH3SOCH3

-1,8

CH3OH

-2,0

(CH3)3COH

-3,8

O 2N

NH2

-4,5

NO 2

(CH3)3N
N

9,80

C2H5OH

-5,1

7,03

(C2H5)2O

-5,1

NH

230

231

5,2

CH3COOH

-6,2

C6H5NHCH3

4,85

C6H5CHO

-7,1

C6H5NH2

4,60

CH3COCH3

-7,2

2,64

N-

2-

NH2

-8,27

3-

NH2

2,47

2,4,6-

NO2
O 2N

O2N

4-

O2N

-9,41

NH2
NO2

NH2

(C6H5)2NH

0,99

CH3CN

-10,1

0,8

C6H5NO2

-11,3

CH3NO2

-11,9

231

232

232

233

3.3.3. -

3.3.3..
() (+),
-

2,3 RT.pK = -2,3 RT lgKa = GTo,

GTo - ,
.. +2 -+3+ ++2 +3+
. =298 , 2,3 RT=1,36 /,
G293Ko=1,36 (/).

(3.16)

(Ho)
(So) - ,
:
GTo= Ho-So.

Ho So, ,

, .
, , G
" () (":
G=G-G.
G ,
; G ,
, . H, S
" ", G. , G
H S .
"" "",
- .
. , , (),

(G), .
, . H<0,
, H>0, . S
, GH,
. , S

233

234
,
,
. , S0 Sconst,
, " " , ..
. ,

, (H),
(D), (H) ..

.
. , ,

, .. . ,
KCl , H>0. -
, , S,
H G . H/
, S-
( ), G/ - ( ).
;
.
,
, . ,
0 . ,
S0=( S0 - S0 ).

. , H.
, ,
.. :
S=S+S+S,
S - , (
);
S - , -
;
S - , ( ,
..).

, [S=S,

234

235
-S, >0], , S<0,
, S0.
:

(CH3)2C=CH2 + H2O ( So=37.7 /.)

(CH3)3COH

O
3H2=
O

1,3,5-

(S=83,6 /.)

(S= -47,8 /.)

( -)

H
C

H3C

COOCH3
C C

C
COOCH3

H3C

- (S0 = 0.5 /.

,
.

, . :

Cl

Cl

[2.2.0]

(So = 4.9 /.)

-1,5 (S=16.8 /K.)

, ,
, S .

H3

CH3
(S=0.4 /.)

-1,2-

CH3
-1,2-

,
1-5 ,
, .

235

236
2
2

(S= -3.7 /.)

5

1-

, ,
(.. ,
; , HCl =1, Br2 =2,
=4, =6 ...).
,
. ,
.
S ,
, , ,
S > S > S

3.3.3.. -

. 3.4
, .
3.4

25

So,

-TSo,

Go,

/.

*
,

5,03

-0,7

-25,3

7,6

6,9

, 3

4,76

-0,2

-21,9

6,5

6,3

, 65

4,20

0,1

-18,7

5,6

5,7

3,75

-0,1

-17,4

5,2

5,1

, CNCH2COOH

2,47

-0,9

-14,3

4,2

3,3

1,26

-0,1

-6,0

1,8

1,7

0,23

-1,0

0,3

0,3

(3)3

CHCl2COOH
, CF3COOH

**

236

237
, 65

10,00

5,5

-27,2

8,1

13,6

3-, 3-NO2-

8,36

4,9

-21,8

6,5

11,4

7,15

4,7

-17,1

5,1

9,8

4,09

2,6

-9,8

2,9

5,5

0,71

-1,5

-6,0

1,8

0,3

C6H4OH
4-, 4-NO2C6H4OH
2,4-, 2,4(NO2)2C6H3OH
, 2,4,6(NO2)3C6H2OH
***
, C2H5NH3+

10,68

13,7

-3,1

0,9

14,6

NH4+

9,25

12,5

-0,5

0,1

12,6

, 6H5NH3+

4,60

7,4

3,7

-1,1

6,3

2-, 2-Cl-

2,64

6,0

8,1

-2,4

3,6

C6H4NH3+

* 26 .
** 23 .
*** 21 11 .
(..
). 5
, , (TSo)
. So ,
, , - ,
(
).
: o>0,
o ,
. .
, , ,
(
),
. o
So ,
, (109 105 ; .
. 3.4).

237

238
,
o. So
So=0.
So>o, ,
, o>>So. , -, :
,
.
, ,
:

AH + H 2 O

H 3O

+ A

BH + + H 2O

H 3O

+ B

( , )
,
, ,
.
,

, , .

S.

3.3.3..

, : 1) , 2) , 3)
. ,
- .
S ,
.

,
.. "" (S) (S+) ( S S+

).

<~-2

. , " ",

238

239

. , , 6 (
=6; . . 3.2), (
-3 -7, . 3.2, ,
). - ,
(2,86 1,26 ; . . 3.2), : 0,1
11% ( 1,96), - 52% ( 1,29).
,
, HCl H2SO4.
, (. . 3.3),
, HNO3 HCl .
, HNO3 HCl .

, , .
, <5, .. , ,
, . ,
, ,
. .
. 3.5.
.
()>16. NH2-K+, C2H5O-Li+ CH3OCH2-Na+
, NH3, C2H5OH
CH3SOCH3 -. ,
C2H5NH2, , , -, .
, , , ,
, . , H2SO4
:

H2SO4 + ArNH2

HSO4 + ArNH3

, ,
:

H2SO4 + HNO3
H2SO4 + RCOOH

HSO4 + ON(OH)2
-

HSO4 + RC(OH)2

3.5
25 ( )

239

240

a ()
2

-7

1,2

2,0

0,71

3,8

-0,3

CHCl2CH

1,26

6,4

5,9

3-NO2C6H4NH3+

2,47

2,89

1,30

C6H5COOH

4,20

9,1

11,0

CH3COOH

4,76

9,1

12,6

5,21

5,55

4-NO2C6H4OH

7,15

11,2

10,4

NH4+

9,25

10,8

10,5

C6H5OH

10,00

14,2

16,4

(C2H5)3NH+

10,72

10,9

9,0

CH3OH

15,5

18,2

29,0

H2O

15,7

18,6

31,4

33

35,1

HCl

NH

( )

CH3SOCH3

, ,

. ,
, .
, ,
,
. , , ,
. , ( )
CH3SO3H HNO3 ( ) (CH3)3CO-K+ NH=C(NH2)2
- ,
, .

, () (),
HCON(CH3)2. ,
, .

. ,

- . . 3.4 ,

240

241
16 ,
3-4103 . 3
, , , 12000
. 5 5
, 2500 ,
8.105 NH4+ 2,5.107 (25)3NH+.
,
- 4-6 .
.

(SH+), ..
:

H + S

+ SH

,
- :

RCOOH (ArOH) + S

RCOO (ArO ) + SH

, ()
(, )
. . 3.6
.
3.6
(; =1)

78,7

25

94

-2

109

20

HCONH2

1,2-

9,8

,
20

CH3COOH

HCN (.)

95

21

CHCl3

4,8

20

47,9

18,5

2,23

20

CH3SOCH3

46,7

25

2,28

20

37,5

20

CH3CN

241

242

36,7

25

512

1,8

20,3

36,1

20

NH3 (.)

21

-34

CH3OH

36,7

25

C2H5OH

24,6

25

- 49

17,5

25

12,7

25

HCON(CH3)2

C6H5NO2

(3)3
.

.
. ,
160 , 2,4,6 ( ) 13 000 (. . 3.5).
(
; . . 3.3),
, .
, , ,
.

. " "
, ,
,
" ", ,

. 2.3.1 (. 2) , ,
,

:
OH...O > OH...N, NH...O > NH...N > SH...X, XH...S >
> PH...X, XH...P > CH...X, XH...C,
- .
, - . , ,
, - NH- (, ,
)
.
- NH-.

242

243
. -
- - - ( + +I ).
, .
- - ,
, -, , -,
.
(
-) , ,
,
:

O -

O H-OCH3

-O

O -

-O

O H-OCH3

N
N

O -

, -,
, , -, ..
, .


, ,
. , (17)
, (18).

BH +

+ B

()=29, =10,5, ..
1018 .
-
. 19

243

244
,
. ,
, , ,
,

.
(. . 3.2).
3- ,
, , .
,
( , . - ).
"-" "",

.
, , ,
,
, . , HF F-
. :
+

2HF + H2O

H3O + (F...H-F )

HF2- , F-...HOH, , F- ,
, HF
, .
.

,
, .. .
.
(. . 2.1.3, . 2),
(,

CH3COO-NH4+),

O
CH3 C

H
N

, , , , ,
.. ,
10-12; , . 3.5,

244

245
, .
(, , , ,
..) , .
,

, ,
. ,
,
,
( ). (
): , - -
, - ,
Na+ (3)3- ( ).

. -

125 , - 11 . ,
- 125/11=11,4 ,
. 400 , 19
500 - . , 49-
, , 11,4 ,
4,3- , .
, -
, ,
, .
, ,
,

.
, .

(. 2.1.3). , ,
. , -
, ,
.
, , , .
, ,
. , ,
, , ,

245

246
, ,
, .
, ,
2,
.

-- (. 3.5,).
,
,
2 ,
, (. 3.5,).
,
-- , ,
, -- (. .
2.2, . 2). ,
.

. 3.5. , () ()

. 3.5.. , ( )
( S-O) , ,
. 3-,
(
-, (+)- -- , NH2
- -NH3+),
. ,
.

3.3.4.

246

247
.
(. . 3.2) (. . 3.3),
(3.15) (
+, - ) , , , =7 (=10)
0,1% ([A]/[HA]=10-3), (=4,6) 0,4%
([B]/[BH+]=251).
, 8-,
:

+ H3O

+ H2O

(pKa=9,9)

N
O

OH

+ H3O+
+

+ H2O

(pKa=5,1)

NH

N
OH

OH

7,5 , , ..
, , , =4,4 84% 8-
, =10,9 91% .
, , .

,
. (3.15)
, ,
(. . 3.3.2). (3.15) .
1932 .
, ("
"). ( + + +) (+)
(. . 3.3.2):

1 BH +
a HS + B

(+)=lg

B
-lg
BH

(3.18)

- ; HS+ - .
HS+, , ,
, , .
( ),

247

248

, [B]/[BH+] ((3.18))
. [B]/[BH+]
I; .
- 1 2,
, . 1 2
, . (
1 2, ,
- I1 I2 - ,
, I=0,1 I=10). (3.18) 2 (3.18)
1,
(+)=lg( B H + / B1 )-lg( B H + / B2 )+lgI2-lgI1,
1
2
I1 I2 - 1 2, .
I , ,
, 1 2 lgI1 lgI2
H2SO4 (. 3.6,).
, lgI=lg( B H + / B1 )-lg( B H + / B2 ) HS+ , ,
1

lg( B H + / B1 )-lg( B H + / B2 ) HS+.

1

. 3.6.
() , ()

248

249
14
B1/B2, B2/B3, ..., B12/B13, B13/B14 (. 3.6,)
- (1) 2,4,6- (14),

- 98%- - . 1,
lg( B H + / B1 )-lg( B H + / B2 )=0. ( 1
1
2
2, 2 3 ..,
1 14 ; . . 3.6,) ,
H2SO4, ..

BH / B
+

, .

,
,
.
2/H2SO4
0 100% , .
3.6, ,
. . 3.6, ().
(3.18)
(+)=-lgho-lgI=Ho-lgI,

(3.19)

ho= =-lgho. ,
. ho=[3O+], ..
ho=. ho>>[HS+]. , 50%- (`7,5 M) H2SO4 =3,38 .. ho=4000. 100%- (18,8 ) H2SO4 =-12,1, .. ho=1012,1.
,
. 3O+,
, . ,
,
,
4 .

H2O

O
H HH

OH2

OH2

, ,
.

249

250

:
pKa(B1H+)-pKa(B2H+)=lgI2-lgI1.
, pKa(BH+),
, pKa
. - (pKa=0,99; . .
3.3). 2,4- pKa=-4,53, 2,4,6- pKa=-10,1.
. ,

.
100% , . . 3.7
, 100%- H2SO4.

(R+), (ArH2+),
(AlkH2+) ,
.
3.7.

( )
H2SO4

12,1

H2SO4-SO3 (3:1) ()

13,6

FSO3H

13,9

H2SO4-SO3 (1:1) ()

14,4

ClSO3H

12,8

FSO3H-SbF5 (1:1)

17,5

HF

10,1

HF-SbF5 (9:1)

20

CF3SO3H

13,0

HF-SbF5 (1:1)

>20

CF3COOH

3,05

. ,

BH / B
+

(
).
, .
, ,
( . 3.6,).
(+)=-lgI. , , ,

250

251
. -,
,
, . :
+

O
R

O H

H2SO4

R C
NH2

NH2

-N- ,
:

H2SO4

OH

: N,N- ('''), (HI) ,
HCl, HClO4, HF, FSO3H ..
HR+,
H2SO4:

ROH + H

R + H2O

R Ar3C.

H R + = lg

aH 2O R +

aSH + ROH

= pK R + lg

R+
ROH

(3.20)

KR+ - R+ . KR+
R+
. , R+
(. 3.6,).
KR+, , . 9.15 (. 9).
- . ""

,
. ,
, , _ ("
").

, , , . ,
, , :

251

252

NC

CN
(NC)2C=C(CN)-C(CN)2

NC

CN

pKa = -8,5

CN

pKa < -11

()
, .
(, ,
) ,
,
(0,001 ) (CH3)4N+OH-
.
, :

NO2

NH2

NO2

+ OH

NH + H2O

(H2O)

_ , , ..

=_-lgI
H-=.

252

253
_
/2 . 3.7. 52,2
.% _=17,7, 90 .% _=26,2. ,
_
.

,
,
. _
CH-, NH- -.

-,

-
.

3.7.

. -
. 3.15 (. 3.5).

0,01

4N+OH ,
. (_30)
65-70 .
( ):

CH3 SOCH3 + N aH

C H3 SOCH2 N a

+ 1/ 2H 2

- .

3.3.5.
1960- 1970- -
, -
,
, .

253

254
, ,

, , ..
. ,
,
() (. . 3.3.3,).
,
,
, .
.
,
.

,
():
- () + + () (), = -(-);
() + + () + (), = -()
, ,
+.
. 3.8 ()
. ,
, . ,
:
+ + +, = -42 /;
+ + +, = -124 /.
, (
): ,
(NH3, H2O, HF .),
- (4). ,
"" :

H
H3C +
(Ho= -126 /)
H

H3C-H + H+

3.8

, /

254

, /

255
CH4

126

CH3-

416

SiH4

146

SiH3-

369

NH3

2007

NH2-

400

PH3

185

PH2-

386

AsH3

175

AsH2-

356

H2O

164

HO-

391

H2S

170

HS-

3553

H2Se

170

HSe-

339

HF

131

F-

371

HCl

140

Cl-

333

HBr

141

Br-

323

HI

145

I-

313

CH3O-

379

2=

168

CH3OH

182

(3)3=

202

C5H5OH

187

325

205

CH3COOH

188

(25)2

205

CF3COOH

167

179

HCCH

152

2=2

159

178

187

33

147

(. 3.8),
(= -416 /). -, ((HI)10), , . ,
:

-

, - ,
= , = (,

> ,
, - > - - >

, - (,

, , )
)

-++ .
1 ( 1+) - 2-

255

256
( 2) .
, , G
. HF,
:

HF

298K

+ F

Ho(HF)=371 /,
So(HF)=19 /K.,
Go(HF)=366 /.
Go=366 / (HF)=268 ( (3.16)),
(HF) 3,18 (. 3.2).
. 3.9. So, Ho Go . ,
So , .
, Go Ho, .. ()

, , HCl .
; ,
. (=54
NH3 HNO3) (50
HI).
. 3.8 . 3.9 . ,
.
,
. , ( )
, : HI>HBr>HCl>HF. ,
4 , .
, - ,
(. 3.3.3.).
3.9

/
*

So,

o,

Go,

/.

()

)
(. 5.4)

NH3

25

400

392

287

33

H2O

22

391

384

281

15,7

256

257

CH3OH

22

379

378

273

15,5

C6H5CH3

22

379

372

273

41

C2H5OH

22

376

369

271

15,9

(CH3)2CHOH

22

374

368

269

17,0

(CH3)3COH

22

373

367

268

18,0

HF

19

371

366

268

3,18

CH3SOCH3

24

375

366

268

33

10

CH3CN

26

373

364

267

25

11

C6H5C=C-H

26

370

362

266

21

12

CH3COCH3

24

369

361

265

20

13

C6H5NH2

24

367

360

264

27

14

CF3CH2OH

26

364

357

261

12,4

15

C6H5COCH3

23

363

356

261

19

16

CH3NO2

23

358

352

258

10,2

21

356

350

256

16,0

17
CH2

18

H2S

21

353

347

254

7,0

19

HCN

25

353

346

253

9,21

20

C6H5OH

23

351

344

252

10,0

21

CH3COOH

23

348

341

250

4,76

22

C6H5COOH

23

339

332

243

4,20

23

HCl

18

333

328

240

-7

24

CHCl2COOH

21

328

322

236

1,26

25

HNO3

23

325

317

233

-1,4

* . 3.2.
**

257

258

; dpKa()/dpKa(H2O)0,8,
.. . , ,
, ,
- -
(.
3.3.3.). , ,
-,
, ,
- (
),

).

, .

3.8.

3.9.

: - HHal; -
-; - -.
HBr HI
,
Goo
-.
. , ..
:
HNO3>CHCl2COOH>C6H5COOH>CH3COOH>C6H5OH>CF3CH2OH>AlkOH
, ..
.
.
CH3OH >
( ) 15,5

H2O>

C2H5OH >

15,7

15,9

(CH3)2CHOH > (CH3)3COH

17

18

, ,

, (+I)- ( 2.2.1), (
) , .. .
:
(CH3)3COH>(CH3)2CHOH>C2H5OH >CH3OH> H2O
()

268

269

271

258

273 281

259
(+I)- ,

3 < 25 < -37 < -49
,

( )
, .
, (. 2.1.2), ..
:
++ -+-

++ -+
+
++ - -

,

CH3NH3+ > C2H5NH3+ > (CH3)2CHNH3+ > (CH3)3CNH3+.
, , ..
:
Alk

Alk
- +
+
--+
- +

O-

-+
--- ++
-+

O-

,
( .. ), .
, , ,
( ""
) ,
"- "

.. , , -,
: HNO3, , , 2,2,2. , ,
, .. . , ,
(-I)- CF3 , ,
,
, .
,
, . ,
(652-), , ,

259

260
(652-...).
(652-Na+) NaOH,
.

3.3.6. -
,
, . -

(lgk) , (. . 3.3.4).
lgk . 3.9.

. 3.9. lgk

, , ,
- , , .
"" ( ,
). ,
, ,
7, ,
, :
. ,
, . ,
-
, - , , .
. 3.9 1,
[H3O+] [OH-].

260

261

3.3.6..
,
. , ,
, . :

()

1
-1

()

2,
. (.. ),
, ,
.
. ,
:
1[] = -1[] + 2[].
,
= 2[] =

12
1 + 2

(3.21)

1
z +1

z=-1/2 - , ,
, .
2>>1 (.. z0), (3.21) :
= 1[].
, , ,
( )
(. 3.10,). ,
, .
, ,
,
. , ,
, . : ,

+D

D , .

261

262

. 3.10. (R - , I , P - ). - k2>>k-1; - k-1>>k2. G# -

D ,
D (D1, D2, D3...) . ,
,
:
= [33][-].
, :
k

CH3COCH3 + OH

(CH3COCH2)

, k-1>>k2 (z

Hal2

CH3COCH2Hal

).

= (k1k2/k-1)[] = k1k2[] .
,
( k1),
(. 3.10,). D,
, ,
:

+D

2;

= k1k2[A][B][C].

:

262

263

OH

O
CH3

CH3

OH

+
OH

+C2H5OH

CH3

2;

OH
OH
O

C2H2

O
CH3

+ H2O
OC2H5

z0,5, .. I
, (3.21) ,
:
1
-1

+
=

k 1 k 2 [ A][ B][ D]
.
k 1 + k 2 [ D]

[A] [B], [D]

. ,

k-1>>k2[D]

, k2. [D] ,
, k2[D] , k-1,
k1, [D] , :
[A] [B].
[D] .
,
, .
,
(, ).

3.3.6..
(O, N .)
(. . 2.3.2, . 2);
R RH+, RH+
P.

R + H 3O
+

RH

K1

R H + H 2O

263

264
,
= 12[R][H3O+].
, , RCOOR
. , , , ,
, [H3O+] .
[H3O+] ,
, [H3O+]:
= 12[R]
, ;
,

[H3O+] (. 3.9).
[H3O+] (..
), .

, , NH4+ , 32+
, H3SO4+ 100%- H2SO4 .. ,
, ; , -
.
,

[OH-] (.. ), ,
. , ,
:

K1

RH + OH
-

R + H2O

= 12[R][H-].
:

O
CH3 C

()

OH

OH , H2O

CH3HCH2 C

O
H

(3-)

264

265
, ,
; , -
(, 3- 3, CH3SOCH2- ..).

3.3.6..
, ,
. ,
:

CH3

OC2H5
OC2H5 + H2O
OC2H5

CH3 C

+ 2C2H5OH
OC2H5

, .
, *. , 3+
- (). ,
, ,
3+, , , "",
:

,
( -)
(- ).
. 0,01 HCl 7
4. HCl ,
, 4,75 4,74.
265

266
OEt
C OEt

CH3

1;
-EtOH, -H2O

OEt
H2O

H
OEt

CH3

OEt

OEt
A

OEt

OEt
OH

-EtOH, -A

CH3

+
OEt

H
OEt

CH3

OEt

2;

3;
-EtOH, -H2O

1=2,1.104, 2=1,7.10-3 3=10-7 /..

,
, (-, ),
, (3+).
, ,

=

i[HAi].

,
=

i[i],

i - , .
:

O
CH3

CH3

OH , CH3COO , H2
2
k

CH3COOH

,
. ,
- - (. . 3.5.1).
.
, -, ,
:

266

267

O
CH2 C
H

ki

O
CH2

BiH

Bi

(, )

=i[RH][i],
RH - , , -.
i,
RH .
.

, .. -:
H3O+
H2=CH-OC2H5
H2O

CH3-CH-OC2H5(CH3-CH=OC2H5)

CH3CH=O + C2H5OH

.

,
i-:

H3O+

H3-CH=OH

H2O A 2

CH2=CH-OH + H3O+

=12[R][H3O+][i-].
K ai =

H 3O + Ai
HA i

=ai12[R][i].

,
(3.22)

i.
, , ,
. [i] [H3O+],
[i-], .. [i] [H3O+], [i-] (
[R]). -- .
- :

267

268

K1

RH + OH
-

k2

R + HBi

R + H2O
P + Bi

=bi12[RH][Bi].
,
, .
R i:

R + HAi

K1

R....HAi P

=12[R][i].
, ...i ,
, .. ,
. , :

HOOC

HOOC

C CH2 COOH

COOH + CO2

Al3+;
, - :
O
+
HOOCCOCH2COO + Al3

CH2
C

HO

Al
3

O
-CO2

CH2

HO

CH3
C

C
O

Al

Al

-
. ,
.
(R-CO-)-, -
, .
, ( 245),
(N 102 ), (N 57) (N 195),
:

268

269

Asp-102

His-57

Ser-195

NH CH CO
NH

CH CH2 CH2

NH CH CO

CH2

O
O

H O

H-N

R'O

CO
CH2 C

NH

O H

R'O
CH2

CH2 C

N--H

O H

CH2

CH2 C

H-N

C R
O

CH2

CH2

CH2
R

-RO-

CH2
O
O
C
R
H
O
H

CH2
O
H O
C
H2O
R

..

3.3.7.
1920- ,
, AiH ( Bi) ( ),
() . ,
( )
.
.
:
lgka=lgKa(AH)+const,
lgkb=-lgKa(BH+)+const,
ka kb - ,
; Ka(AH) Ka(BH+) - ; -

269

270
, BH+,
. lgKa=-,
lgka=-Ka(AH)+const,

(3.23)

lgkb=Ka(BH+)+const.

(3.24)

Go -

G# ( 3.3.7.)
.

AH + S ()
R() + AH

ka

Ka (AH)

A- + SH+, Go= RTpKa(AH)

G#= - RTlgk a

R...H...B,

c
R

-G# Go.
:
+

1/Ka(BH )

B + SH ()
R() + B

kb

BH+ + S-, G= -RTpKa(BH+)

R...H...B,

G#=- RTlgk b

c
R

G# Go

( G# Go (. 3.4.5).

3.3.7.


R RH
(. 3.3.6.). , ,
, RH
(. 3.11,).
RH

270

271
+, R-H (RH+Bo)
(R...H...Bo) - (BoH++R-)
( ; (. 3.11.).

. 3.11. (),
() ()
Bi.
BiH+ +, Bi
(, Bi - ; ,
, , i=, =3-), BH+ ,
(.
3.11,). G# RH+ RH+Bi
G
+ BiH+.
, . 3.11, :
G#=

tg
G,
tg + tg

..
lg[kb(i)/kb(0)]=

tg
lg[Kb(i)/Kb(0)]=-[pKa(BH+)-pKa(BoH+)].
tg + tg

, (, ,
) RH BH+ .
. 3.12, 0 1, ..
01 RH+B R-+BH+

01 R+ R++-.
RH, =0 (. 3.12,),
. ,

271

272

RH ,
, .
, 0, 0,
. +, =1 (. 3.12,).

, "" + .
, 1 (1)
( ).
, 0<()<1 (. 3.12,).

. 3.12. . - tg0;
(R...H...B) (RH+B). . - (R+BH+); tg1
,
. () ,
, ,
. () ,
.


-
( ) ,
( ; . 3.3.6.),
.

R + H 3O

K1

RH

+ H 2O

272

273

RH+ + A-

k2

P + HA

(3.22)
=().1.2

lg=lg+lg1+lg2
(3.24) ,
lg= -lg()+const.
,
lg=(1-)lg()+lg1+const.
1 ,

=1-

(3.25)

.
,

kAH
AH + B

BH + A

BH + A

kA-

B + HA

,
lg=lg-lgka= -pKa()+pKa(BH+),
=/- - + ++-.
(3.23),
lg-=(1-)()+lg(+)+const.
, 1-, -
.

3.3.7. ()<0 ()>1

c ( ).
,
, .
.
, .. ,
( )

273

274

.
. 3.12, ,
, ,
.

.
, . 3.12,
,
. , =-0,48:

R2CHNO 2

OH ,
H2 O

( R2 CNO 2 ) + H 2O (R = H , C H3 )

1--2-
-
, =1,68:

H
ArCH2

H...OH

OH

C NO2

ArCH2

CH3
ArCH2

C
CH3

CH3

O
O

N
O

+ H2O

(3.25) , = -0,68. :
, , ,
? ,

, , ?
=1,68 = -0,68 =0,5,
C2H5NO2 ?

1--2-

,
Ar , (). ,
(,
) ,
, .. , (. . 3.11).
,
.

274

275
,
. .

3.3.7..
() ,
0 1:

AH + B

[A....H....B]

BH+ + A-

(.. -
),
(1). ,
, (
), (, =0
; . ). ,
.
, ,
, .

3.3.7..
.

:
G#=H#-TS#

(3.26)

# , .
: G#=
-2,3RTlgk. ,
, ,
, S#=S (
) - S () . S (
3.3.3.), S# ,
.
,
, S#
.
. 3.1.
275

276
3.10.
log S#

()

logA

S#, /.

15-17 (-1)

+8 +17

12,5-14 (-1)

-3 +4

9-13 (-1)

-20 0

9-10,5 (/.)

-20 -15

7-11 (/.)

-30 -10

5-9 (/.)

-40 -20

- +

>CX-CY< >C=C<+XY

+ -

+- -+

# S# :
=-Ea/RT,
Ea - ,

lgk-1/T);

. :
#=-nRT,
n - ,

A=(kT/h)eneS#/R,
k - ; h - ; R - . logA
. 3.10.
( ) .

3.3.6. 3.3.6.,
,
.
:

(OH2)m-1

(OH2)n

(H2O)m+n

R+H++(m+n)H2O

R+H++-+(m+n)H2O

276

277
, -

. , 15-20
3

/(.) 10 -104 .
,
?
,
.
-, ,

. ,
. ,
,
:
OEt
+

OEt + H3O

CH3

CH3

EtO...H...A

OEt + HA

CH3

OEt + EtOH
OEt

OEt

OEt

OEt

OEt

CH3

OEt

CH3

OEt

OEt

OEt

CH3

OEt + EtOH
OEt

(G#) ,
- ,
,
- -.

3.3.7..
,
. ,
1013 -1 ( ),
, 5.109 /(.) ( ), ,

. ,
, , , ,

277

278
, , , ,
..
-
, -
.
:

O
Nu

+ CH3

C
H

k1
k-1

O
CH3

OH

C H
Nu (I )

+ HA

k2

CH3

C H + ANu

(3.27),

Nu- - ; k=kAH[AH] -
I-. I- Nu-
(k-1 . 3.11) I- (kAH[AH])
C2H5S- (. . 9.5., . 9), ,
. I-, k-1 .
I- , C2H5S-; ,
k1.
k1, (
=0).
3.11

Nu

-1 (-1)

C2H5S-

6.106

CH3O-C(O)-CH2S-

7.107

. . 3.12

I-

ArS-

108-1010

0,16-0,26

-
()

RSH

0,7

CF3CH2H

1013

0,30

(+CH2=O)
-3
I-, .. -1 .
G#-1 , (2) . , I-
Nu-,

278

279
(3.27), I- -1. Nu=
32S- -12 ( , ..
). [AH] (3.27)
. ,
, .
. 3.10,.
2 (5.10-9
/(.), .. ), (.
3.10,), . ,
.
. 3.11. ArS-,
:

S
( ) . -1
, I-
. I- ,
. .
,
, .

(1). :

O
CH3

+ H-A

O...H-A
CH3

C
H

OH

CH3

O ...H-A
C Nu

Nu

CH3

C Nu
H

RSH .
-1 , .
, Nu-
( ):

279

280

RSH + CH3CHO + HA
+A

kc

RSCH(CH3)OH +

AH + RSCH(CH3)OH

,
(). : =0,7.
(.. 3.11)
I- ,
:

HOCH2CF3
H C O

+_

(I )

H
( CF3CHOH)

3.4.

, ,
. , ,
, , ,
, ,
-, ..
(. . 13). ,
. , , ,
,
, .
. 1930- .
, .
, -
, ,

3.4.1. -

280

281
- -
25 ( (3.28)), Z:
COOH

COO

H2O

+ H2O

+ H3O

25oC
Z

(3.28)

, ,
Z ( ,
- ).

:
Z=pKa(C6H5COOH)-pKa(ZC6H4COOH)

Z=lgKa(ZC6H4COOH)-lgKa(C6H5COOH)/

Z. ( (3.28))

.
; , :
Z
pKa(ZC6H4COOH)
Z

m-OCH3

m-F

m-NO2

p-NO2

p-CH3

p-OCH3

4,20

4,09

3,86

3,49

3,42

4,37

4,48

0,12

0,34

0,71

0,78

-0,17

-0,27

Z . 3.12.
3.12.
( ), (3.18)

-CH3

-0,06

-0,17

-OH

0,13

-0,38

-C2H5

-0,07

-0,15

-OCH3

0,11

-0,28

-CH(CH3)2

-0,07

-0,15

-OC2H5

0,10

-0,24

-C(CH3)3

-0,10

-0,20

-OC6H5

0,25

-0,32

-CH2C6H5

-0,18

-0,11

-OCF3

0,40

0,35

-CCH

0,20

0,23

-O-C(O)-CH3

0,39

0,31

-C6H5

0,06

-F

0,34

0,06

281

282

-CH2Si(CH3)3

-0,16

-0,21

-Cl

0,37

0,22

-CH2OCH3

0,02

0,03

-Br

0,39

0,23

CH2OC6H5

0,03

0,07

-I

0,35

0,28

-CHO

0,36

0,44

-Si(CH3)3

-0,04

-0,07

-COOH

0,35

0,44

-SH

0,25

0,15

-CN

0,56

0,66

-SCH3

0,15

-CF3

0,43

0,54

-CF3

0,40

0,50

-CF(CF3)2

0,37

0,53

-S(O)-CH3

0,52

0,49

-NH2

-0,16

-0,66

-SO2-CH3

0,60

0,72

-N(CH3)2

-0,15

-0,63

-S+(CH3)2

1,00

0,90

-N(CF3)2

0,40

0,53

-SF5

0,61

0,68

-N+(CH3)3

0,88

0,82

-IO2

0,70

0,76

-N3 ()

0,37

0,08

-N=N-C6H5

0,30

0,35

-N+N

1,76

1,96

-NO2

0,71

0,78

-C(O)-CH3

0,21

-C(O)CF3

0,35

0,14

3- :

ZC 6 H 4 CH 2 CO O H + H 2 O

ZC 6H4CH2CH2COOH + H 2O

3-

H2O,
25o C

H2 O,

Z C 6 H 6 CH 2 CO O

+ H 3O

Z C 6H6CH2CH2COO

+ H 3O

25o C

-2-.

(ZC6H4CH2COOH) pKa (ZC6H4CH22COOH) pKa (ZC6H4COOH) (

), (. 3.11), ..

lgKa[ZC6H4(CH2)nCOOH]=Z+const (n = 0,1 2).

282

283

. 3.13.

. 3.14.

25

Z==0,
const=lgKa[ZC6H4(CH2)nCOOH],
..
lg

( )
= Z
( )

(3.29)

pKa( )-pKa( )=Z, -

. 3.13. (0,49 ArCH2COOH 0,21 ArCH2CH2COOH).

(3.29)

,
.
O
P

COOH

OH
OH

, (3.29) :
lg(KZ/K0)=Z,

(3.30)

K0 - , KZ -
- - .
(3.30) . .
- Z - Z .
- -

283

284
(
25, =1).

3.4.2.

.
, , ,
. ,
(. 2.2.1): (-I) (-)-
,
(-I)>(+M) (-M)>(+I) >0, (+I) (+M)- <0.

. - -Z
, (
Z
; . 2.2.1). -
,
,
. - , ,
.
, lg(KZ/K0)>0 KZ>K0. ,
, .

. =0,49, ..
, (=1 ); 3 =0,21, .. .
, 3- Z , 3 - ,
.
.
,
, ;
:

25

3CN

(ArCOOH)

1,0

1,85

2,36

2,41

2,48

284

285
.
.
,

, .

N + C6H5SO2

NSO2C6H6, =+3,76

Z
Cl

25oC

SO2

, = -2,07

n-ClC6H4N=NSO2
Z

,
ArN2-, ArSO2-.

3.4.3. .

,
Z . 3.12, ,
(. 3.14). : - , (+)- , - (-): NO2, CHO, CN .. , -
,

. (-)-
, :
O

(
)

-
, :
O

285

286
, ,
, , ,
, .
, -
, ,
, - (" ").
- , - Z=NO2, CHO, CN ..
(. 3.14). - . 3.13;
; ,
-, (=2,77).
- :
O

NH3 + H2O

NH2 + H3O

NH3

NH2

3.13
- -

=--

-NO2

0,78

1,27

0,49

-CN

0,70

0,88

0,18

-C(O)-CH3

0,48

0,84

0,36

-C(O)-OC2H5

0,45

0,74

0,29

-CHO

0,44

1,04

0,60

-COOH

0,44

0,78

0,34

-CCH

0,23

0,52

0,29

-C6H5

0,08

0,08

C6H5
ZC6H4

C6H5 + H2SO4

KR

C6H5

ZC6H4

C6H5 + HSO4 + H2O

OH
, Z - (, Z = -3),
KR+ .
+ (" ");
13 .

286

287
,
.
lg(Z/0)=Z,

(3.31)

Z - Z; 0 -
.

3.4.4.
1950- , ,
,
. , 1930 ,

(. . 18.8.2, . 18):

OH
R

C OR

C OR

OH

OH2

, , -,
, ,
, ( ,
). ,
()-.
, ,

(.. ) ,
.
, ZCH2COOC2H5
lg(CH2Z/CH3)B-lg(CH2Z/CH3)A=*CH2Z *,
CH2Z - ZCH2COOC2H5; CH3 -
(CH2Z=CH3; ; *
(" ") - ,
CH2Z , CH2Z CH3. *
,
*=2,48.

287

288
* I, ("
"), *
I(Z)=0,45*(CH2Z)
I (
, -,
). .
1. 4- [2.2.2]-
50%- 25:
COOH

pKa (Z=H)-pKa(Z)=1,65 I(Z)

Z

2. 25:
ZCH2COOH; pKa(CH3COOH)-pKa(ZCH2COOH)=3,816I.
3. (F) -19F -
:
F

ZF-Z=HF=7,10I-0,60

I . 3.14.
3.13.

-CH3

-0,04

-SCH3

0,23

-C6H5

0,10

-S(O)-CH3

0,50

-C(O)-CH3

0,28

-SO2-CH3

0,59

-C(O)-OC2H5

0,30

-F

0,50

-CN

0,66

-Cl

0,46

-CF3

0,45

-Br

0,44

-NH2

0,12

-I

0,39

-N(CH3)2

0,06

-Cl+-C6H5

1,72

-H-C(O)-CH3

0,26

-Br+-C6H5

1,63

-NO2

0,65

-I+-C6H5

1,35

288

289

-OCH3

0,27

-OC6H5

0,38

, , , , ..
(-I)- , , I.

3.4.5.

,
() ,
(Go G#). ,

).

.
, , , , Go= -RTlnK,
:
Go=Go+const.
:
GoZ=GoZ
.
Go
Z Go.
Z Go
, , , Go.
, ,
Z, :
Go GoZ


.
,
, (.
3.3.7). (3.23) (3.24) lgk
, lg - . ,
.

289

290
- - , ,
,
:
lg(Z/0)==[pKa(C6H5COOH)-pKa(ZC6H4COOH)].
,
lgZ=-pKa(C6H5COOH)+[lg0+pKa(ZC6H4COOH)],
Z 0 -
.
( Z).
, , =.
, . 3.3.7.,
( 0,
). ,
.
.

(,
), ( )

. , , , , , , ,
, Z.

.
,

,

. ""

3.15.

. -

( ),

=0

(. 3.15).

, . =1 - .

290

291

- (, NaNH2/NH3 (.),
(C2H5)3NOH, ..:
#

CH2...H...B

CH2-H + B

CH2 + BH

,
.
"" ( . 3.15),
ZC6H4CH2-, Z ,
Z
||. "" ( 1 . 3.15),
,
Z , || .

(|
| ), (||
). , ,
, , .
.
( ||)
, , , .
,
. .
.
,
, 105-106 . ,
,
,
. . ,
(. 13) Br2 106
, Br2 ,
;
, .
,
(,

291

292
2; . . 10.2, .10). ,
,
( ||)
( Z).
, , ,
, , , .
, Z
,
..
.
, -
. , ,
/. ,
.

3.5. -
, ,

) .
, , , ,
.
, ,

-,

Z, :

Z C:

C H+B

+ BH

,
-

() , , ,
_ ( 3.3.4). -
. 3.15, -, NH-
, (. . 3.3.5).
, , ()=35,1,
.

292

293
-, ..
-, .
3.15.
- ( )

() ,

6H5CH(CN)2

4,2

(-)

C6H5COOH

11,4

339

()

CH2(CN)2

11,1

336

1,1-

CH3CH(CN)2

12,4

HCN

12,9

353

HCl

13,0

333

(CH3CO)2CH2

13,3

344

- (-)

(CF3)3COH

13,8

(-SH)

H2S

14,7

352

15,5

1,3-

SO2
SO2

CH2

CH2(COOCH3)2

15,7

348

CH3CH2NO2

16,7

357

CH3NO2

17,2

358

18,0

356

18,2

CH2

(-)

C6H5OH

18,2

351

HF

19,9

371

(-NH)

C6H5NHCOCH3

19,3

20,1

20,5

353

CH2

CH3

NO2

N (-NH)

NH2CSNH2

21,1

C6H5CH2CN

21,9

352

. . 3.5
293

294

22,6

353

CH2

-()

(C6H5S)3CH

22,5

(-)

CF3CH2OH

24,0

261

C6H5COCHCH3

24,4

C6H5COCH3

24,7

363

(-NH)

CH3CONH2

25,5

26,4

O
CH2

CH3COCH3

26,5

369

(-NH)

NH2CONH2

26,9

C6H5CCH

28,7

C6H5SO2CH3

29,0

(-)

CH3OH

29,0

379

(-)

CH3CH2OH

29,7

366

-()

[(C6H5)P]2CH2

29,9

CH3COOC2H5

30-31

371

(C6H5)3CH

30,6

-()

(C6H5S)2CH2

30,8

C6H5SO2CHCH3

31,0

31,1

1,3-

S
S

CH2

CH3SO2CH3

31,1

366

CH3CN

31,3

373

(-)

H2O

31,4

391

(C6H5)2CH2

32,1

364

- (-)

(CH3)3COH

32,2

373

CH3SOCH3

35,1

375

H2

36

401

(-NH)

NH3

41

400

C6H5CH3

42

379

CH2=CH-CH3

43

291

294

295

(-NH)

44

NH

C6H6

45

397

C6H5SCH3

49

CH4

55

417

3.5.1
-
.
(, N) . , 3+ 1,4.1011 /.,
. - N- 3+
- NH- -
, 3+ -. . 3.16.
3.16
25

N /

(/.)

H3O++OH- 2H2O

1,4.1011

H3O++CH3COO- H2O+CH3COOH

4,5.1010

H3O++NH3 H2O+NH4+

4,3.1010

H3O++4NO2C6H4OH H2O+4NO2C6H4O-

3,6.1010

OH+NH4+- H2O+NH3

3,4.1010

CH3CH2COOH+CH3COO- CH3CH2COO-+CH3COOH

2,9.108

HOCH2CH2SH+-SCH2COO- HOCH2CH2S-+HSCH2COO-

1,5.107

CH2ClPO3H-+C6H5P(CH3)2 CH2ClPO32-+C6H5PH+(CH3)2

1,2.107

CH3NO2+OH- CH2NO2-+H2O

2,8.101

10

H3O++(CH3)2C=CHOH H2O+(CH3)2CH-CH+OH

5,9.10-1

, 3+ - ,

295

296
, ,
( ):
H

O
H

OH

O
H

H OH

H n

3+ -.
, 3+ -
. 3+ - - .
.

(. . 3.3.3).
,
. , ,
, .
7 8 . 3.16, S...H-S .... N,
, 1-6. - ( 9) -
( 10) .
, , .
, ,
, , :
+
B

O
C

#
O
C

+B

O
O

COO
+ BH

103 ,
,
, ,
. ,
, , ,
.
.
, 2,6--- (I) 3+ 100 ,
. ,
, .

296

297

1,8--()-

(II)

2,7-

(III):
N(CH3)2

(CH3)2N

N(CH3)2

(CH3)2N
H3CO

(CH3)3C

OCH3

C(H3)3
III

II

(CH3)2N
,
.
.
:
CH3

CH3
N

CH3

CH3

CH3
N

CH3

CH3

CH3

1,8-()
. , III =16,3 (. .
3.3). . 1,8-() " ".
[1.1.1]- (IV):
- 1,4.10-8 /(.),
(V) :
O

O
HN

NH

O
O
IV

H
O
O

,
. - , ,
, ,

297

298
- (. 3.3.3).
. 3.16.

"", "" - NH-. ""

(1899 .), (
9 . 3.16).
- ( -) . ,
- .
- , -

, ,
.
,
.
() .

, .
, .
-
, .
- ,
, "" .
:
C6H5C

CH + B

C6H5C

+ HB

65- sp- , , - .
, () :
C

CH2

"" .
, , -
"", .. .
-
,
.
. ,

298

299
(, ). ("") , -
:

D ( ) + N H 2

NH3 ()

+ N H2D
NH3

H + OD

H + N H2

+ H OD
D2 O

RD + O D

(. 3.3.6.), - RD
- :

RD + B
=

k1
k -1

R ...DB

k2

R ...HB

RH + B

12
[RD ][ B ]
1 + 2 [HB ]

2>>k-1, - ,
1[RD][B-].

-: . 1
.
() (.
3.3.7):
lg1=- pKa+const.
lg1 - -, pKa -
. lg1, - ,
. pKa, -, ..
.

3.5.2.
-1>>k2, k2, =1/-1, ..
-.

pKa , .

299

300
, 1, ,
k2, .
-
:

H + B

+ HB
k2

D + B

+ DB

[R- ... H ... B +]#

[R- ... D ... B +]#.

, -
:
R-H ... B
R-D ... B-.

() R .
, + , D+ ( , +).
, /kD,
().
1, /kD .
, /kD1, , 1, ..
/kD 7-8 (/k=17-20), /kD=10-12 (/k=2830). , () -
() /kD>10. ,
- , ..
, ,
.

300

301

3.5.3.

3.5.3..
, , 3-,
sp3- sp2- :
H
H
H

, , sp3- ,
- -. sp3-,
-, sp3- 25% s-, s-
, - (. 1).
.
,
()
- , .

. 3-
5 /:
( ~ 5 /)

. ,
2- 2 -70
20% (.. 60% ,
40% - ), 0 .
, (. . 19)
,
. -70 2
, 0
:

301

302

Li
H
C6H13

C
CH3

1. CO2

1. CO2

2. H3O

2. H3O

C6H13
H

COOH
H
C6H13

CH3

C
COOH

CH3

2-
(2-)

. ,
. ,
60 109,5 .
,
120, 60.

-2-

(..

) -2- :
H3

H3
H

Li

H3

H
H

1) CO2
+

2) H3O

COOH

H3
H

1--2,2-
:

H
H

Ph

Ph

Ph

Ph
C

CH3O-

Ph

N CH OD
3

H
H

Ph

, ,
. ,
, , ,
:

302

303

R1
R2

R2
R1

R3
N

R3

, ,
, , - : COR,
NO2, CN .. , 1--2,2-,
2--3-
:

CH3

CH3

CH3O

C6H5CH2 *C C N

C6H5CH2

C CN

CH3OD

CH3
C6H5CH2 CD C N

- -N ,
, sp2- ,
:
C6H5CH2
CH3

,
, .

3.5.3.. s-
,
,
s-. , - (
)
, , s-.
s- , s:

303

304
s-, %:
s-

100

sp-

50

sp2-

33

sp3-

25
0

p-

,
s- ,
:
H
H

<

~
~

<

RC

sp3

sp2

sp

- (. 3.15).
s- - :

, s- - . ,
s- ,
. , ,
--- .

kH/kD=6,5)

- , :
-

0,00 ()

-3,13

-4,62

-6,51

-7,20

-7,96

(VI), (VII), [3.1.1.02,6] (VIII) .
(s- - 30-32%)
. VII VIII s- - 40-41%
:

304

305

VI

VII

VIII

3.5.3..
, (-I)- .
, , ,
(CH3)4N+ -, :
(CH3)3N+-CH3 + C6H5Li (CH3)3N+-CH2- + C6H6
(+I)- ,
- :
4>->->-.
,
64-. ,
, -. 65-, -
(sp2). : -
, sp2-
. , ( )
( )
:

sp2- - , ,
, 64- (, -CN, -NO2 -COR)
.
.

() , (-I)-
->->-, .. --
, --.
DC6H4X + KNH2 (NH3) C6H5X

305

306
( =1,00):

(1,00)

CF3
10

10

0,14

0,23

10

10

10

CH3

10

0,23

,
. ,
-.

3.5.3..
,
. .
- ,
.
2 2-CH>3CH>4-CH.
- :
- 4, 4-CH>3-CH>2-CH. ,
- ,
:

(1,00)

F
6

0,7.105

10

10
10

1.2 10

0,3.105

2
(C2H5CD=C5H5ONa, 140oC)

:
-,
-.

, (. . 2). sp -,
, sp2-
,
.

306

307
, ,
. ,

, , 2, 3 4
r2:r3:r4=1: 3 :2.

r3

r4
N

r2

(lgk) :
lgk ( 3) - lgk ( 2) = r2/r3 = 1/ 3 =0,58;
lgk ( 4) - lgk ( 2) = r2/r4 = 1/2=0,50.
: 0,58 0,42 ,
.
N- , ,
.
: 2-CH>3-CH>4-CH.

-4
10

-4
3.10

(1,00)

Cl

CH3
N-
( 2 )

3.5.3.3..
, (-)-, , ,
( , ), . , (-)-
.

O
C N

O
C N

307

308

C C

C C

-, ,
,
.
, ,
. ( )

,
.
,
. IX
sp3-, -
. -.
,
,
(=5,26 ):

(IX)
O

[2.2.2]-2,6-;
;

(X)

1,3-;
;

- (-)-
(. . 3.15):
NO2>COC2H5>COCH3>SO2C6H5>COOR>SO2CH3>C6H5.
,
- . (
; . . 3.17),
- .
3.17
, (-)-
-

CH3NO2

11

17,2

CH3CN

308

(25)

31,3

309

CH2(NO2)2

6,6

CH2(CN)2

12

11,1

CH(NO3)2

,-1

CH(CN)3

(-5)

(-7)
()

CH3COCH3

(20)

26,5

CH2(COCH3)2

13,3

CH(COCH3)3

8,9
( )

, -COR, -CN -NO2, ,

N.
.
( =18,; . . 3.15)
.

-- (. . 12)
:

, ,
. ,
,
, .
.
:
H
H

Ph

()
=22,5
( )

CH

H
Ph

Ph

C CH C
Ph
Ph
1,1,3,3-
~15
( )

9-
=18,5
( )

309

1,1,3,3--()
~10 ( )

310

CHH2CH

Ph

CH

CH-

H
CH
Ph

1,3-
=13,2
( )

-()
=6,2
( )

=15 ( )
=13,5 ( )
=13,8 ( )

1,1,5,5-()-1,4
=8,8
( )

, ,
,
. ,
(. 12). ,
- , - :

(10-)

(10-)

(14-)

(14-)

,
(. 12).
CH3

CH3

CH3

1,2,3-
~62 ()

4-

,
, .
,

(, ), ,
- (. 3.15):

310

311

CH2
H
H
:
~36 ()

CH CH3

~43
( )

,
-. - d-:

- d-
p-d

NaOD D2O
, 106 , . P+(CH3)3 -N+(CH3)3 ,
, , ,
, .
,
2- 3d :
CH2

CH2

CH2

, d, , ..
.
-d- ,
.
, () (XI) -:

Ph3P CH2 PPh3 + B

(XI)

pKa=5,60

Ph3P CH PPh3

Ph3P C PPh3

3.5.3.. ,
,
. ,
NaOH.
;

311

312
- - ,
:

CHCl3 + OH

-H2O

Cl + :CCl2

CCl3

- ,
.

.
, ,
CHI3<CHBr3<CHCl3<CHF3. .
-

CHF3

CHCl3

CHBr3

CHI3

()

26,5

15,5

13,7

13,7

. ,
, - :
, , ,
.
d- . ,
,
d- - - ,
-d (.. 10 )
:

X
X

X C

:C

(X=I, Br, Cl, F)

,
(+)-, ..
( ) :

( X=F >>C l, Br)

( )
- , ,
, .
,
,
-d-.

312

313

3.5.3..
,
. ,
, , .
-
(. 3.3.3.).
. =16 , 21
- , 28,7 - .
- .
,
:

C6H5C

+ -

CH + K A

C6H5C

- +

C K + AH

, , ,
.

3.5.3..

, , ,
, , .
1926 . . - - -
, ,
.
, ,
.
, ,
-.
, ,
, , ,
<15 <2040
, .. .
,
, .

z1 z 2 e 2
, - ,

a

313

314
, 2k, k . ,
, ,
,
.
,
. ,

,
. : ?
, , r<rc
, , , r=rc
. rc

rc =

e2
. , rc
RK B T

2.
,
( , ) .

.
: 1) ,
2) ,
.
,
.

, .
,
, .

, -.
, , - - , .
-
.

SN1 . 19501960 . -

314

315
(. 9),
SN1.

. 1965-1966 . - .
.
-
. , , - F-Na+ 25
356 , (50) 373 .
, - (C6H5)4BNa+, Na+.
,
.
F-Na+ ,
, .
,

. ,
- , :

F-M+ + nS

F-SnM+,

S - .

. -20 -50
373 ,
- .
,
,
. max , ,

- ,
.
. , , ..
, 50 -70
. K-,
Rb- ,
. ,
-30,
0 - .

315

316
Li+>Na+>>K+>Rb+>Cs+>NR4+.

,
-
(. 3.18).
3.18
max
25

rc,

max,

0,60

349

Na

0,96

356

K+

1,33

362

1,66

364

3,8

368

4,5-5,0

373

374

Li+
+

Cs

NBu4

, -
,
,
- .
.
, (), , ,
- Li-, Na- - ,
. ,
,
-.
, ..
RM.


- - Ar3C-M+, - Ar2CH-M+, ArCH2-M+, - RCC-CH-R-M+, - ..
, - ,
, ,
.
, , , .
, , , 1/r, r -

316

317
.
.
,
.

max

1/r - , .
,
(. 17).
,
, , N-, ,
, , .
,
.
- ,

, .
, ,
, -,
F-M+S ( S -
-). ,
, .
, ,
, - .
1,2--1 1,3--1,
,
-
-.
-
,

.

317

318

4.

4.1.
4.2.
4.3. -
4.4.
4.4.1.
4.4.2. ,

4.4.3.
4.4.4.
4.4.5.
4.4.6.
4.4.7.
4.4.8.
4.4.9.
4.4.10.
4.4.10..
4.4.10..
4.4.10..

,
- .

,
,
. CnH(2n+2);
- H(CH2)n-H. ,
CH2,

, CH2- ,
.

,
- .
, .. n
. (CH2-CH2)n,
- (.
5), , -
.
.
318

319

. ,
70 95%. C1-C40
,
, ,
. C27-C37
. C29H60
, C27H56 C31H64 .
4.1.
4.1

, C

, /

CH4

- 162

- 183

0,415 - 165C

C2H6

- 88

- 183

0,561 - 100C

C3H8

- 42

- 188

0,583 - 45C

-C4H10

- 0,5

- 139

0,579 0C

- 12

- 160

0,557 -25C

9,5

- 16

0,613

36

- 130

0,626

28

- 160

0,620

69

- 95

0,660

62

- 153

0,683

2-

2,2-
-
2-

-
2-

CH3
CH3 CH CH3

CH3
CH3 C

CH3

CH3

-C5H12
CH3 CH CH2 CH3
CH3

-C6H14
CH3
CH3 CH CH2 CH2 CH3

-C7H16

98

- 91

0,683

-C8H18

126

- 57

0,702

106

- 100

0,656

2,2,3,3-

CH3 CH3
CH3 C

C CH3

CH3 CH3

319

320

2,2,4-

CH3
CH3 C CH2 CH CH3
CH3

99

- 107

0,692

CH3

-C9H20

151

- 53

0,718

-C10H22

174

- 30

0,730

-C11H24

196

- 26

0,740

-C12H26

216

- 10

0,748

-C13H28

235

-5

0,756

-C14H30

254

0,762

-C15H32

271

10

0,768

-C16H34

287

18

0,776

-C20H42

343

37

0,788

-C30H62

66

0,779

-C40H82

-C50H102

-C60H122

99

-C70H142

105

-C100H202

115

235
1 . .
260

81

3 . .
420

92

15 . .

4.1.

.

.
.
,
.

.
,
.
, .
320

321

.
, , ,
.
-, -, -, - .. ,
, .
:
CH3

CH3

CH3 CH2 CH2 CH2 CH CH3

6

CH3

CH3 C CH2 C

2-

CH3

CH3

CH3

2,2,4,4-

CH3

CH3

CH3 CH2 CH CH2 CH2 CH3

1

3-
CH3

CH3 CH2 CH2 CH CH CH2 CH2 CH3

CH3
4

CH3
4

CH3 CH3

CH3 CH CH2 CH2 CH CH CH2 CH3

CH3 C CH2 CH2 CH2 CH3

3

CH3
2,3,5--4-

CH3
2

CH2

2--4-

CH2 CH3
3

CH3 CH2 CH3 CH3

CH3 CH CH2 CH CH2 CH3

CH3 CH2 CH CH CH CH CH3

CH3
2,3,4-
CH3

5--4-

CH3 CH CH CH CH3
2

CH3

2,5,6-

CH3
2,2-

,
, ,
:
CH3 CH CH2 CH CH CH3

CH3

CH3 CH3

2,3,5-
CH3 CH CH2 CH CH2 CH2 CH CH3

CH3

CH3

CH3

2,4,7-

321

322

, :
CH3 CH CH3
CH CH3
CH3 CH2 CH2 CH2 CH CH2 CH2 CH2 CH3

5-(1,2-)

4.2.

, , .
, - sp3 , C H
sp3- 1s- (.
. 1). C C 1,540,01, C H
1,0950,01. .
- - , ..
- . -
-
, sp3-
.
,
- ,

.
.
, .
,
,
.
.
,
.
, .
, .

322

323

. , .
.
,
. ,
, .
.
,

.
H

H
H

HH

H
H

. 4.1

H
H

( -

. 4.1. ()
()

, ).

.
( : - -).
.
, ,
,

.
-
,

. ,

323

324

, 2,9 /.
60
C H:
=60

=0

HH

60

H
H

H
H

G = 2,9 /

2,9 /
C H
,
1 /.
.
;
1 /.

.
,
C C , ,
C C ,
.

=0,

=60.
:
E = Vne + Vnn + Vee + E,
Vne C H
CH3 ; Vnn , Vee -
C H-; E .
Vne,
.
.
( Vne),

324

325

( Vnn + Vee + E) .
Vne 19,7 /. ,

. ,
22,4 19,7 =
2,7 /.
2,9 /.

,
.

-,

, ..,
, , , , . ,
, , .
,
.
-.
1,3- 1,4-, . (
. 24.6 . 24).
. 4.2
.

HH
H
H

HH
H
H

H
H

2,9

60

60

H
H

2,9

2,9

-60

H
H

H
H

H
H

HH

H
120

120

180

H
H
H

240

300

180
240

300

. 4.2.

325

326

2,29,
2,55.
2,9 / G= RT ln

25

(. 4.2).
4.2

50

50

55

45

0,119

60

40

0,240

70

30

0,502

75

25

0,651

80

20

0,821

90

10

1,302

95

1,744

98

2,305

99

2,722

99,9

0,1

1,092

25 (/)

25 99%
1% - .
, , ,
(
) C H C
CH3 :
CH3

H 3C H

60

H
H

= 3,4 /

H
H

, ,
3,4 /.

326

327

1 /,

3,4 - 12 = 1,4 /.

4.3. -

.
,
C(2) C(3). ,
. () ()
.
. ()
,
.
.
(),
180. .
( ) 60
. .

C(2) C(3). H H CH3 H,
, , () , ()
(), 21,4 + 1 = 3,8 /.
() (). () ()
5,4 /
(). 3,4 /:
5,4 /
H H (.. 5,4 21 = 3,4 /). ,
. . 4.3

C(2) C(3) -.
327

328

CH3

CH3

H3C H

H3C
H H
CH3
()

H
H

H
H
H H

H
H
()

()

CH3

H3C CH3

H3C

H
H

CH3

H3C H

CH3

H
H

H
H
()

()

H H
CH3

()

H
H
CH3
()

- () () 0,9 /
- (), -
, , .
(. . 2, . 2.2)
() () (

).
H3C CH3

H3C H
H3C
H

H
H

H
H

H
H

H
H

H
C
H3
()

()

()

H3 C H

5,4

3,8

3,8

0,9

0,9

180
-180

-240

120
-120

CH3

60
-60

0
0

60
60

CH3

120
180
120
180

CH3

CH3

H3C

CH3

CH3
()

()

()

CH3
()

. 4.3.
C(2) - C(3) -

328

329

(), 0. -
, 5,4 / ,
- -. 25

72%

-.

28%

G
. . 4.3
.
4.3

, /

HH

1,0

H CH3

1,4

CH3 CH3

CH3 CH3

3,4

0,9

, , .
- ,
- :
H

H (C12H26)
H

(),
- .

(-)

329

330

. 2- -.
3-, 4-
- -
.

H
H, H CH3 CH3 CH3, . 4.3. . 4.4
2 .

2-

.
, , (),
0 120, ,
CH3 H H H. ,
(3,4 + 1,4 + 1,0) = 5,8 / (. .
4.3), 6 /.
() 2- CH3 H (31,4
/) 4,2 /. () -
- (),
- CH3 CH3.

330

331
H 3C H

H 3C H

H
H

CH3
CH3
H
H

H3C CH3 H3C

H

CH
H 3
H
H

CH
H 3

H 3C H

CH
CH3 3

6,0

-240

-180

4,2

6,0

1,8

60
-120

120
-60

0,9

180
0

0,9

240
60

CH3
H3C
CH3

300
120

360
180

CH3
H

6,0

CH3

CH3

CH3

CH3

CH3

. 4.4. 2-
C - C

. , , - 2,3 , :
CH3

CH3
H

CH3

H3C

CH3

H
CH3
CH3

CH3
-
(
)

-
(
)

.
, 2- (. . 4.2, 4.3
4.4) , ,

331

332

, .
, ,
(), (), (),
.

.
,
.

.
,
, .
,
,

.

, ,

.

4.4.

:
A.. B

A + B..

A.. B
A.. B

A.. + B

.
A + B

C H
, ,
. , ,
, - CH3+ - H-

332

333

314 /, .. .
:
.

CH4

CH3

H + e

CH3 +
CH3+ +
H..

H + H; H = + 104 /
e- + H; H = + 226 /
+ H; H = - 16 /

CH3+ + H + H; H = + 314 /

CH4

C H
,

() .
.

4.4.1.

200 -
, :
CH3 + Cl2

200 h

CH3Cl + HCl + H,
H = - 25 /

CH3Cl
HCl .

CH3 H; H = + 104 /

CH3 Cl; H = - 84 /

Cl Cl; H = + 58 /

H Cl; H = - 103 /

H = + 162 /

H = - 187 /

H = 25 /.
,
,
, .

,
: CH3Cl, CH2Cl2, CHCl3 CCl4.

333

334

, .

.
.
1.

,
..
2. .

Cl Cl.
3. , ,
.
.
4. ,
, ,
. 5

O O (. . 2.6),

:
R +O

( )

,

.
5. (C2H5)4Pb
.
(. 19) - .
C Pb (31 /)
Pb(C2H5)4
Pb + 4 C2H5.

Pb(C2H5)4

334

335

.
t

Cl2

2 Cl + H; H = + 58 /

Cl Cl, C
H , Cl Cl C
H . .
,
:

Cl + CH4

CH3. + HCl + H; H = + 1 /

CH3. + Cl2

CH3Cl + Cl + H; H = - 26 /

,
, :
.

Cl + CH3
.
.
CH3 + CH3
.
.
Cl + Cl

CH3Cl
CH3CH3
Cl2

;
,
CH3 ,
. , :
.

Cl2 + H; H = - 58 /

Cl + Cl

(. . 4.6). ,

Cl. + CH4

HCl + CH3

H Cl C H ,

CH3 + Cl2

CH3Cl + Cl

C Cl CH3Cl Cl Cl.
. 4.5
.
,

335

336

.
, CH3
,
. ,
G1
G2 , .. G1 > G2. ,

. ,
.
H

. :
H = +1 26 = -25 /.

4.4.2. ,

, ,
.
,
. ,
F2 > Cl2 > Br2 > I2.
CH3X . 4.4.
4.4

1.

X2

2.

X . + CH4

2X

CH3. + HX

CH3X + X.

CH3. + X2
3.

H, /

.
X +X

X2

336

F2

Cl2

Br2

I2

+37

+58

+46

+36

-33

+1

+16

+33

-71

-26

-24

-20

-37

-58

-46

-36

-104

-25

-8

+13

337
CH4 + X2

CH3X + HX

,
H
, H .
.


, .
.
HF (166 /)
,
, CH3 F,
6 /:
CH4 + F2

CH.3 + F . + HF + 6 /

,
,
F2

2F

,

F F.
, , .

. ,

,
.

.

,
.
,

337

338

, *.
CF2Cl2 -12; CCl3F -11;
CClF2CClF2 -114; CCl2F2CClF2 -113; CHClF2 -22.
CHClF2 (-22) CF2=CF2,
-4 ()
.
-235 238

235

UF6

238

UF6.

,
.
. ,
.
.
(III).
CoF3 ,
(II):
C nH 2n+2 + CoF3

C nF2n+2 + HF + CoF2

(III) , CoF2 .
, .
:
H1 = +16 / ( H1 = +1 /). ,

[Br---H---CH3]
[CH3---Br---Br]
G1 = 18 /

G2 = 2 /

HBr + CH3
H1 = 16 /
H2=-24 /

Br + CH4

H = -8 /
CH3Br + Br

x=0

x=1

. 4.6.

,
. , -,
.
*

338

339

G1
, . , G1
(18 /; . 4.6)
G1 (4 /).
(- 24 /)
(- 26 /) G2
.
G1 ,
, .
300
500 .
:
G1 = 34 /. G1 ,
(H1 = +33
/). , ,
,
300. HI
CH3I CH4 I2.

, G1 G2
,
,
G1.
.


: ,
.
,

.

339

340

4.4.3.

,
,
,
.
C C,
C H. ,
C H. ,
C H,
,

. ,
C H. (.
. 4.4.10) , .
.
, .

1-

2-

3:1. , 500
3:1.
. , , CCl4
25, ,
43% 1- 57% 2-:
CH3CH2CH3 + Cl2

h
CCl4, 25

CH3CH2CH2Cl + CH3CH(Cl)CH3
(43%)

(57%)

,
. C H
CH2- 3 / , C H-
CH3-.
,
.

340

341

. C H :
57 : 2
=
= 4 :1
43 : 6

2- 36% 2--2- () 64% 1--2-:

CH3 CH CH3 + Cl2
CH3

Cl
CH3 C CH3
CH3

h
CCl4, 25

CH3 CH CH2 Cl
CH3

(36%)

(64%)

H-

C H-, 5:1:
36 : 1
=
= 5 :1
64 : 9

,
> >
, (. 4.5).
4.5

CH3-

CH2-

CH-

200

3,9

5,1

300

3,3

4,4

600

,
()
() .
, .. , .
(. 4.7).
,
,
.

341

342

(CH4)

(Cl 3p)

(CH4)

. 4.7. ,
.
(. 1.17).

( )
(. 4.8) -
( C C).

(Cl 3p)

. 4.8.

,
(C3H8) (Cl).
, .

,
, . ,

342

343

2. ,
C1 H C2 H (. ).

,
,
,
. ,
, :
CH3
CH3 C CH3
CH3

+ Cl2

Cl2

CH3
CH3 C CH2Cl + HCl
CH3
Cl

+ HCl ( 57%)

,
. , , -
330 92% 2- 8% 1-:
CH3CH2CH3 + Br2

330; h

CH3CH2CH2 Br (8%) + CH3CH(Br)CH3 (92%) + HBr

:
CH3CH2CH3 + Br.
CH3CH2CH3 + Br.

CH3CH2CH2 + HBr + H, H = + 10,5 /

- ( )

CH3CHCH3 + HBr + H, H = + 6 /
- ( )

,
. , , 2,2,3-
97% , ,

:
(CH3)3C

CH CH3 +
CH3

h
Br2 CCl
4

343

(CH3)3C

CH3
C CH3 (97%)
Br

344

200 1 CH3-;
90-100 CH2- 1600 CH-.

:
(Cl) , (Br) .

(. . 3, . 3.4.5).
(H = -5
/),
(H = +10 /). ,
, .
,
,
.


, , .
. 4.9

1 2.
C H
.
C H
.

344

 G = 2.5 /

345

C HBr]

CH3CH2CH2 + HBr
3 /

(CH3)2CH + HBr

CH3CH2CH3 + Br
x=0

x=1

G = 1 /

C HCl]

CH3CH2CH2 + HCl
3 /

(CH3)2CH + HCl

CH3CH2CH3 + Cl
x=0

x=1

. 4.9.
() ()

,
,
1 2 2,5 /,
, 3
/.
1 /,
. ,

.

345

346

4.4.4.

,
> > ,
C H- (.
4.6):
RH

.
R + H + H

C H ,
3 /.
H ,
.
(CH3)3CH (CH3)2CH-CH2 H (98 /)
(CH3)3C H (92 /)
.
:
> > .
,
, -:
.

C6H5CH2 ~ CH2=CHCH2 > (CH3)3C > (CH3)2CH >

> CH3CH2CH2 ~ CH3CH2 > CH3 > CH2=CH > C6H5

.

2 .

; ,
C
H c 2pz-, .

,
.

346

347

C H -, , ,
.
H
H

H
4.6

H,

H,
/

HH

104

CH2=CHCH2 Cl

69

HF

136

C6H5 H

110

H Cl

103

C6H5 F

125

H Br

88

C6H5 - Cl

97

HI

71

C6H5CH2 Br

82

FF

38

C6H5CH2 H

87 (85)

Cl Cl

58

C6H5CH2 Cl

70

Br Br

46

HCC H

125

II

36

CH3CH2CH2 H

98

H3C H

104

CH3CH2 - CH3

85

H3C F

109

CH3 - CH3

88

H3C Cl

84

C2H5 - CH3

85

H3C Br

70

(CH3)2CH - CH3

84

H3C I

56

(CH3)3C - CH3

81

H3C OH

91

CH2=CH - CH3

97

H3C SH

70

CH2=CHCH2 - CH3

74

H3C NH2

80

C6H5 - CH3

102

H5C2 H

98

C6H5CH2 - CH3

72

H5C2 Cl

81

H5C2 Br

68

H5C2 I

53

H5C2 OH

91

HO H

119

(CH3)2CH H

95

HO OH

51

(CH3)2CH Cl

80

CH3O H

102

(CH3)2CH Br

68

CH3S H

88

(CH3)2CH OH

91

C2H5O H

103

(CH3)2CH I

53

CH3C H
O

CH3C CH3

347

86

77

348
(CH3)3C H

91

(CH3)3C Cl

79

(CH3)3C Br

65

CH3CH2O CH3

81

(CH3)3C I

50

NH2 H

107

CH2=CH H

108

H CN

130

CH2=CH Cl

88

CH2-CHCH2 H

87

,
, .
- (, NH2), - (, - BH2) ,
,

(, - CH=CH2)

. ,

X :
X XCH2

H2B

CH3

NH2

CH=CH2

CCH

CN

Cl

11

10

21

15

11

,
/
, CH3
, (X = CH3, Cl),
(X = CH=CH2).

. ,
p-.
, -
20. ,

C H:
H
H3 C
H3 C

CH3

H3C
H3C

348

CH3
( )

349

C H ,
-
.

. :
2 (CH3)3C.
(CH3)2C.

(CH3)3C-C(CH3)3
CH2

(CH3)2=CH2 + HC(CH3)3
()

.C(CH )

( )

3 3

,
.
.

4.4.5.

.
:
O
h

RH + SO2 + Cl2

R S Cl + HCl

:
Cl2

2Cl

RH + Cl.
R. + SO2

R. + HCl
O
R S.
O

O
R S . + Cl2
O

R S Cl + Cl
O

, RSO2Cl
.
349

350

-
SO2:

R + Cl2

RCl + Cl

RSO2

R + SO2

,
SO2, .
.
:
CH3CH2CH3

SO2 + Cl2
h, 50

CH3CH2CH2SO2Cl (48%) + CH3CH(SO2Cl)CH3 (52%)

R-SO3H. ,

RSO2Cl

RSO2Cl + 2 NaOH

RSO3 Na+ + NaCl + H2O

-
.
, SO3- -
. , 8 16 ,
,
.

.
(, , , )
, .
,
.

, -.

350

351

4.4.6.

NO2

, N2O4
150.
, .
NO2

. NO2-
,
. 10 20%-

150
. . 1888 . -
2- 63%.
(, 1936 .).

420 450 , , ,
, .
, 90% 10% .

21%

:
CH3CH2CH3 + HONO2

420

CH3CH2CH2NO2 + CH3CH(NO2)CH3 + CH3CH2NO2 + CH3NO2

(32%)
(33%)
(26%)
(9%)

, C H,
C C, .. .
:
.

CH4 + NO2

HNO2 + CH3

H2O + 2 NO2

HNO2 + HNO3

CH3 + NO2

CH3NO2

NO2
, ,

351

352

CH3
. , ,

NO2.
450.

4.4.7.

500
,
.
- .
-
, , (. 4.7)
CH2 CH2
.

4.7
-

C - C

H, /

CH3 CH3

88

CH3CH2CH2 CH3

85

CH3CH2 CH2CH3

82

(CH3)2CH CH3

84

(CH3)3 CH3

81

.

: . , ,

352

353

CH3 + CH3CH2CH2

600

CH3CH2CH2CH3
600

CH3CH2 + CH3CH2

, ,
, , .
600 , -,

.
.
,
:
.

RCH2CH2CH2 + RCH2CH2CH2CH2CH2CH2R

RCH2CH2CH3 + R CH2CH2CH2CH2CHCH2R

.
(-). -

-
.
, -
:

RCH2CH2CH2 CH2CHCH2R

RCH2 CH2CH2 + CH2=CHCH2R

-

CH2=CH2 + RCH2

..

.
-.
, C C-
, :
-C9H20

C3H7 + C6H13

353

354

- -
:

CH3CH2CH2
CH3 + CH2=CH2
.
.
CH3CH2CH2CH2CH2CH2
. CH3CH2CH2CH2 + CH2=CH2
.
CH3CH2CH2CH2
CH3CH2 + CH2=CH2
.
.
CH3CH2
H + CH2=CH2

C C-
,
.
:
.
.

C9H20 + CH3

CH4 + CH3(CH2)6CHCH3
-

CH3(CH2)6CHCH3
CH3CH=CH2 + CH3(CH2)4CH2
. - .
CH3(CH2)4CH2
H + 3 CH2=CH2

,
-,
, .
(
) ,
. -

.
- ,
400 500
.
750 900
-,
: , , , .
- 700
900:
- C6H14

700 900

CH4 + CH2=CH2 + CH3CH=CH2 +

(15%) (40%)
(20%)
(25%)

1930 1950 .

354

355

(C10 C15)
(C12 C20). ,
, 65, ,
.

.
400 450 10 15 .
(87% SiO2 13% Al2O3),

.
, ,
,
(. . 24).
,
,
.
.


(. . 28).

.

4.4.8

100 150
.
, .
-
:
355

356

RCH2CH2R'

O2
(CH3COO2Mn; 100 150

RCOOH + R'COOH

-:
CH3CH2CH2CH3 + O2

(CH3COO)3Co
170 180; 50 .

2 CH3COOH (50%)

4.4.9.

1929 . .
,

1 2 . . .
500 600,
,
:
.

Pb(CH3)4

Pb + 4 CH3

, ,
.
, .
Pb(CH3)4 ,
.
, , , , .
,
, :

4 CH3 + Pb

Pb(CH3)4

,
, , .

356

357

Zn(CH3)2 Sb(CH3)3,
:

.
.
3 CH3 + Sb

2 CH3 + Zn

Zn(CH3)2
Sb(CH3)3

Pb(C2H5)4 C2H5.

, 0,005 .

-
.

4.4.10

C H ,
,
.. , , , ,
( CH3+),
(NO2+) .. C H-
, , C C
. (.
3, . 3.3.4),
FSO3H
SbF5.
( ),
:
H+(SbF5SOF)-

FSO3H + SbF5
HF + SbF5

H+(SbF6)-

, , , SO2 SO2ClF,
:

357

358

,
.
, , :
CH4 + H +(SbF5SO3F)

CH5+ (SbF6SO3F)

3 ,
.
, , n, n- n-
. -,

- -,
, , -
-. , ,
. 4.8.

4.8

n- (n-

- (-

- (-

, O, S,

N, Hal

(C

H, C C, H H ..)

, : n- > - > . . -, n- (
)
, - -. -, n- , -, ,
- ,
n-:

358

359

( )

,
.

4.4.10..

CH5+, -,

sp3- (
). Hb+ ,
.. C H, ,
:
H

H
C
H

Ha

+ H+
b

C
H

Ha
H+b

Ha
C

+
Hb

H H, ,
. , CH5+
CH3+ - H2.
CH5+ CH3+ H2.

, , ,
:

359

360
H
C
H

CH+
3 + D2

H
C

CH2D++ HD

..

+
H

CHD+2 + H2

4.4.10..

CH5+ ,

H
,

R3 C +
E

CH2 + H+

CH3+

R3 C +

CR3
E

, E = D, H, R, NO2, Hal ,
R3C+ ,
.
,
,
:
.. CH + H+
2

CH+
3

CH3+ ( ,
CH5+), . ,

,
.

, , ,
, .
C H C C

.
( ) (
):
360

361

R3C-H + E+

R3C++ EH ( )

R3C +
E

R3C-CR3 + E +

R3C +

R3CE + H+ ( )

CR3

R3CE + R3C+ ( )

..

. , -,
(. ), -, .

H3+ ,
:
H

+
H

H
H

,
,
. ?
.
. 4.10 ,
.

361

362

+
H

. 4.10.
H+
3

H3+ 1s- ;
- (. 2). 1
. ,
H, 3 ( 1s-).
1

, .
3 , .
2 3 ( . 4.10
) (
). H3+
2 3 , ,
1. , H3+
.

4.4.10..

362

363

.
.

. .
1
:
H

DF / SbF5

+ H+

- 80

FSO3H/SbF5 (-80)
C H, C
C, . , - ,

C CH3 C H-:

H

CH3
CH3 C
CH3

CH3
C CH3
CH3

CH3

C
CH3

CH3

.
R3C+
(, t-Bu+SbF6-), R3C+,
(, R3CH + H+ = H2 +
R3C+).
78 :
(CH3)3C+ SbF5- + HC(CH3)3

SO2ClF
- 73

(CH3)3C-C(CH3)3 + HSbF6 ( ~ 2%)

:
(CH3)2CH + SbF5- + HC(CH3)3

SO2ClF
- 78

(CH3)2CH-C(CH3)3 + HSbF6 ( ~ 12%)

,
, (,
NO2+PF6-) (,

363

364

).

HF FSO3H,
:
RH + NO2+ PF6-

R-NO2 + PF6

CH2Cl2 -

RH

CH4

C2H6

(%)

2-5

10

.
2 5% ( ) 55 60: (
).
: CH3Cl
CH2Cl2, CHCl3 CCl4.
Cl+ C C
CH4 + Cl2

SbF5
SO2ClF, - 78

CH2Cl + HCl ( ~ 2 - 5 %)

:
CH3

CH3

CH3

Cl

CH3

Cl

. , ,

,
-
(, ,
).
- .
(I), (II) (III) ,
, .
,

(III),

,
(I) (II), , , :
364

365

CH3-CH2-CH2-CH3
- H+
H

H
+
CH3 CH CH CH3

+ H+
- H+

+ C2H6 -C2H6

+ H+

+CH CH
2
3

+
CH3 CH2 CH CH3
-H 2

+H 2

+
(II) CH3-CH2-CH-CH3

C - H
CH2 H
+
CH2 CH CH3

+
CH

- C4H10

CH
+ 2 5
CH3 CH2 CH CH3
H

+C2H6
- C2H6

- C2H6

+C2H6
,

" "

CH3
+
CH2 CH CH3

" "

CH2 CH CH3

+ C4H10

C - C

CH3
+ CH

CH CH3 (I)

CH3
+
CH3 C CH3 (III)

CH2

+
CH2 CH CH3

+H2

-H+

(CH3)3CH

" "

365

366

5.

5.1.
5.2.
5.3.
5.4.
5.4.1.
5.4.2.

5.4.3.

5.4.3..
5.4.3..
()
5.4.3.. .
5.4.3..
5.4.3..
5.4.3..
5.4.3..
5.4.3..
5.4.4.
5.4.5.
5.4.5.. HBr,
,
5.4.5.. N .
5.4.6.
5.4.6..

1. ( . . )
2. -
3. -
5.4.6..
5.4.6..
5.4.7.
5.4.8.
5.4.8..
5.4.8..
5.4.8..
5.5.
5.5.1.
5.5.2.
5.5.3.
5.5.3..

5.5.3.. C H

366

367

5.5.4.
,
- . ()
:
H

121,7

1,076
116,6

1,330

C
H

, , 120.
sp2- (. 1, . 1.8).
C H
sp2- 1s- . ,
. 2 (. 2.5.2),
, . C H
(1,076) C H (1,095),
sp3- 1s- .
, sp2-
sp3- . . 2,
sp2- ,
- pz-
.

. - - ,
.
- C C
, - .

,
- -, ,

367

368

:
D

D
C

C
H

D
C
H

450 500,
65 /.
, p-
.
5.1

()

()
-1

CH2=CH2

104

CH3

--2

-2

47

CH3CH2CH=CH2

CH3

57

CH3

61

(CH3)2C=CH2

-7

()
-2

CH3CH2
H

-1

CH3

37

CH3(CH2)2CH=CH2

368

30

169
186

0,
595

130

0,
62

139

0,
604

0,

H
C

0,

50
-6

CH3

. /

110
-

CH3CH=CH2

105

0,
595

140

0,
66

151

0,
64

165

369

CH3CH2

-2
3-

H
C

36

CH3

(CH3)2CHCH=CH2

25

(CH3)2C=CHCH3

39

CH3(CH2)3CH=CH2

64

(CH3)2C=C(CH3)2

73

-1

CH3(CH2)4CH=CH2

93

-1

CH3(CH2)5CH=CH2

-1

CH3(CH2)6CH=CH2

-1

CH3(CH2)7CH=CH2

-1
2-2
-1
2,3-2

0,
65

140
0,

65

137

0,
66

134

0,
68
0,
71
0,
70

12
2

119

0,
72

14
6

0,
73

17
1

0,
74

, -- (. . 8).

,
- -
C2 C3-:
D

D
C

C
H

H 3C

D
C

H
H

CH3
-

H3 C
H
H

H
C

CH3

H
-

65 /,
- - 4 /.

100,
, - -
369

370

230.
. - ,
.
. 5.1.

5.1.
: ,
.. ().
, :
.
:
CH3CH=CH2

CH3 C CH2
CH3

:
H3C

H3C

CH3

Br

CH3

Br
C

C
Br

- . -

, - :
Cl

Cl
C

Cl
C

Cl

C
H

CH2=CH :
CH2=CHCl

CH2=CH-O-C2H5

,
- :

370

371
C6 H 5

C6H5CH=CH2

H
C

C 6H 5

- -.

.

.
. - - :
CH3CH2

H
C

Cl

CH2CH3

3---3-
(3----3)
(CH3)2CH-CH2-C

CH2
CH3CH2CH2

CH2

CH2CH3

2--1-
(2--1)

CH3
2,4--1-
(2,4--1)

- -
,
.
.
, R,S- (. . 8)
,
Z ( zusammen ),
E (
entgegen ).

R,S- 8:

371

372
(1) CH3CH2

(2) CH3

CH2CH3 (1)

(1) Cl

H (2)

(2) CH3

Z-3--3-
(2) CH3

CH3 (1)
H (2)

Z-2--2-

CH2OH (1)
CH3 (2)

(1) ClCH2

E-1--2,3--2--4-
(1) CH3

COOH (1)
C

(1) CH3

(2) H

CH3 (2)

(2) H

CH3 (2)
COOH (1)

Z-2--2- E-2--2-

, , .

, , , ,
OH,

CHO,

COOH,

,
:
4

CH2
CH3 CH2 CH2 OH
-3--1- (3--1-)

5.2.

--

. , ,
-, --2

:
H
C
H3C

CH3

H 3C
H

--2 (85%)

CH3
H

--2 (15%)

G = - RT ln K,
, ,
372

373

--2 1 / ,
-.

- .
- ,

. ,
.

C
H

C
H

C
H

H
H

C
C

H
H

--2

--2

- -
.
, H
:
CH3

H3C

C
C
H
H
H = -28,6 /

H2
Pd

CH3CH2CH2CH3

--2

H2
Pd

H3C

C
C
H
CH3
H = -27,6 /

--2

. 5.1.

--2.
- ,
--2
--2

,
-, G >
G.

. 5.1.
- --2

. - -

373

374

.
C3 C10. , , ,

-, , .
7 -,
-. , -

, -. , -
,
- (. 5.2).

: - > -,
.
5.2

- H ,

23,0

31,2

26,5

23,6

20,7

24,0

24,6

24,5

374

375

H
H

H
-

- -
.
5.3

- H, /

CH2=CH2
CH3CH=CH2
CH3CH2CH=CH2
(CH3)2CHCH=CH2
(CH3)3CCH=CH2
(CH3)2C=CH2
CH3CH2
C CH2
H 3C

28,5

H 3C
C

26,9
CH3

H 3C

CH3

H 3C
C

32,8
30,1
30,3
30,3
30,3
28,4

2669

-, -,
. , . 5.3, ,

, 32,8 /,
, -1 -1 2,5 /.

H.
C

>

R
R
-

>

375

>
R
H
-
H

H
>

R
>

H
R

R
R

>

376

-, -, -
(. 5.4).
5.4
Hf

- Hf, /

CH2=CH2

+ 12

CH3CH=CH2

+5

CH3CH=CHCH3

-2

CH3CH=CHCH2CH3

-7

(CH3)2C=CHCH3

- 10

(CH3)2C=CCH3)2

- 18

(. 2):
H
H C CH CH2
H

,
, .

, sp3- sp2-
. - C H, sp2- ,
, C H- sp3- .
, , ,
-1 .
- Csp3 Csp2 , - Csp2 = Csp2
s-
C C C H. - H3C C
(1,505) 0,03 , C C- , 2Csp3sp2-2Csp2-sp2

2Csp3-H-2Csp2-H (2Csp3-Csp3-2Csp2-Csp2

2Csp3-H-2Csp2-H). ,
Csp3 Csp2 - Csp3 Csp3 -. -2

376

377

Csp2 Csp3 -, -1 Csp2 Csp3 . -2,

.

(Csp2 Csp3)- (Csp3 Csp3)-,
:
sp3-sp2

CH3 CH

sp2-sp3

CH CH3

-2
( )

sp3-sp3 sp3-sp2

CH3 CH

CH CH2

-1
( )

,
sp3- sp2- ,

-
.

5.3.

-
.
.

- - . -
-
.
(. . 10, 11, 16, 17),

.
1.

(. 10):

377

378
H
C C
X

C + BH + X

:
H
Cl
H
H

2.

(CH3)3C- O K

+ (CH3)3COH + KCl

(CH3)3COH ; 100

(88%)

(. 11):
. H2SO4

C C
H OH

C + H2O

. H3PO4 t

:
H

85%- H3PO4

OH

3.

+ H 2O

170

(80%)

(. 10):
Br
C C
Br

NaI Zn
(C6H5)3P

:
C 6 H5

4.

H Br
C C C6H5
Br H

NaI

C6H5

H
C
C + NaIBr2
H (70%) C6H5

. (. 10):
H
C C
+

AgOH ; 150
H2O

C +

..N(CH ) + H O + AgI
3 3
2

N (CH3)3 I

:
CH3 CH2 CH CH3
+

AgOH ; 150
H2O

CH3CH2CH=CH2 + ..N(CH3)3 + H2O + AgI

N (CH3)3 I

5.

(. 4):

378

379

Pt ; t

C C
H H

C + H2

:
CH3CH2CH2CH3

Pt; 500

CH3CH2CH=CH2 + CH3CH=CHCH2 + CH2=CH-CH=CH2 + H2

: , ,
-, (. . 4

28).
6.

- -

(. 6):
R'C CR" + H2

R"

R'

Pd / BaSO4,

0 20

C
H

H
-

R'C CR"

R'C CR"

Na
. NH3 ; 38

R'
C
H

R"
-

Ni(OAc)2 + NaBH4
CH3CH2OH, H2NCH2CH2NH2, 20

R"

R'
C

C
H

H
-

:
CH3CH2C

CH3(CH2)3C C(CH2)3CH3

7.

CH3CH2

Ni(OAc)2 + NaBH4
CCH2CH3
CH3CH2OH, H2NCH2CH2NH2, 20

Na
. NH3 ; 38

. (. . 16):

379

CH2CH3
C

C
(99%)

CH3(CH2)3

H
C

(78%)

(CH2)3CH3

380
R'
C

R'

O + (C6H5)3 P C HR"'

R"

CHR"' + (C6H5)3P=O

R"

:
+

O + (C6H5)3 P C H2

CH2 + (C6H5)3P=O

(86%)

5.4.

- (146 /)
, C
C- (2 88 = 176 /). - C C , , -

-,

. , , ,
,
,
:
CH2=CH2 + H2

CH3-CH3 + H; H = - 32,7 /

CH2=CH2 + Cl2

CH2ClCH2Cl + H; H = - 43,2 /

CH2=CH2 + HBr

CH3CH2Br + H; H = - 19,0 /

CH2=CH2 + H2O

CH3CH2OH + H; H = - 10,9 /

- -.
, . 1 2, -

.,

-,

*- *- C
C, , ,
. , -.

380

381

5.4.1.

,
(. 5.2),

. , ,
.
.

- , , , ,
, BaSO4, CaCO3,
..
.
,
. PtO2,
.
H2PtCl66H2O
(NH4)2PtCl6 .

20 50 , , .

.
, , Pd/C Pb/BaSO4, Ru/Al2O3, Rh/C .
, ,
0 20 .
.


.
.
5 10 .
50 100, .. ,

381

382

, .

:
CH3

+
CH3

CH3
H
(82%)
H
CH3
-1,2-

PtO2
H2 CH COOH, 20, 1
3

1,2-

H2 + CH3CH2CH2CH2CH=CH2
H 3C

PtO2
C2H5OH, 20

COOH
C
+ H2

Pd / C

C
H 3C

CH3CH2CH2CH2CH2CH3 (92 %)

HOOC
H3 C

COOH
CH3
H

H
COOH

-,
.
-. ,
( ),
-. - -
- -.
, - - ,
- - - ().
,
.
.
- ,
,
.

-
.

,
,
-.

382

383

C
.
:
R

H H

R
H H

H H

R
H

C
R
H

R
C
R
H

(C=O, COOR, CN .)

C=C-

, (0 20
. :
:
H2, Pd / C 1
C2H5OH, 20, 1 .

:
CH=CH-COOCH3

H2, Pd / C 1
C2H5OH, 20, 1 .

-2-

CH2CH2COOCH3

-3-

:
CH=CH-CN

H2, Pd / C 1
C2H5OH, 20, 1 .

CH2CH2CN

().

383

384

(I)
(III)

[(C6H5)3P]3RhCl

-()

-()-

[(C6H5)3P]3RuHCl. ,
(III) ( .
).
:
H2

[(C6H5)3P]3RhCl

, 20

-
-
.

:
C

C
H 2C

H2C

CH2

H3C

CH3

H 3C

CH3

H3C

H2

H2C

[(C6H5)3P]3RhCl

H2C
H3C

CH3

CH
C
C

CH3
CH3

-,
-2- -2,3-:
H

CH3
C

[(C6H5)3P]3RhCl

C
H

H
D2

D
D

CH3
CH3
H

CH3

-2-

-2,3-

, ,
, . 27.

384

385

5.4.2.

NH2-NH2
Cu2+ NH=NH.
.
,
.
- .
CH3

CH3
NH2-NH2
H
Ni
CH3
CH3
H
-1,2-

NH2-NH2
2+

Cu + H2O

1,4,6-

(98%)

5.4.3.

-
*-. , (E+)
-, (Nu-) *-
C C.
, .
,
- ,
*-.

385

386

() *

Nu- ()

()

E+ ()

, ,
NO2, COR ., *-,
.
E+
, .

Nu-:
C

+
C +E

+
C

+
C

+ Nu -

(1)

C
Nu

(2)

,
E+ Nu-
. ,
, , ,
, RSCl, NOCl,
BrN3, IN3, I-N=C=O
.
AdE (Addition Electrophilic)

AdE2

( ) AdE3 ( ).
386

387

5.4.3..

,
.
.
,
:
CH3CH=CH2 + Br2

+ Br2

CCl4
00C

CH3 CH CH2Br (99%)

Br
1,2-
Br

CCl4

(95%)

0(-5)0C

Br
-1,2-

CH3CH=CHCH3 + Cl2

CH3CH2CH=CH2 + Cl2

CCl4
-100C

CCl4
00C

CH3 CH CH CH3 (100%)

Cl Cl
2,3-
CH3 CH2 CH CH2Cl (97%)
Cl
1,2-

CCl4
, , ,
.
Br2 Cl2 ,
. ,
,
, .

, ,

-. ,

387

388

, - .
, -
- ;
- -
.
C

..

..

.
+ ..Br
.. .
.. - Br

C
Br +

Br
- ( )

- .

Br Br ( Cl Cl), p- sp2
, (
):
C

+
Br

Br +
Br

Br

, ,
.
-

(vic ).
SN 2 ,
Br
Br.
C

Br

Br

Br

,
,

388

389

.
: 1)
, 2) , 3)
, 4) ,
5) , , 6)
, 7)
() .

, .. .

:
v = k [][Br2] + k [][Br2]2 + k [][Br2][Br-],

v = k [][Br2] + k [][Br2]2
v = k [][Br2].
,

. ,
- Br-, - Br3-,
: Br2 + Br- = Br3-. Br3 . -

.

.
* - ,
. -
- -2, -2, -2, ,

-.

,
;
.
389

390
5
6

Br
2
4

+ Br2
H

Br

Br

H
Br
a,a-
e,e-
-1,2-

-1,2- a,a- (

24),

e,e-.

,
,
.
:
CH3

H 3C
H 3C
H3 C
A

CH3

HO

, B
A C:
H

CH3

CH3
HO

C8H17
H

CH3
Br

Br2
CCl4

HO

CH3

Br

,
-. -
(RCH-CH2Hal)+
.

390

C8H17

391

C- C-, Br-
-, -.

. -,
-
SN 2- (. 9)
:
Hal
+
C

Hal
C

C
Hal

Hal-

- -

-.

, , -
- -2:

H
C

CH3

+ Br2
CH2CH3

H
H3 C

--2

H
CH3

CH3
C
H

H
C

+ Br2
CH2CH3

--2

H3C
H

C
+
Br

Br
Br
CH3
H

(R)

C
(R)

CH2CH3
Br

Br

CH3

CH2CH3

+
Br

Br
C

(S)

(S)

H
CH2CH3
H

C
(S)

C
(R)

CH2CH3
Br

Br

CH2CH3
H

CH3

Br
C

Br

(R)

C
(S)

H
CH2CH3

, , - - -3,
(.. D- L) - ,

391

Br
H

392

Br
H

Br
+ Br2
C
C
CH3CH2
CH2CH3 CH3CH2
CH2CH3
+
Br
--3
C

CH3CH2

(R)

CH2CH3
Br

H
Br

+ Br2
CH2CH3

CH3CH2

H
H

--3

(S)

H
CH2CH3

(S)

H
C
(S)

C
(R)

CH2CH3
Br

Br

CH2CH3

+
Br

Br
C

Br
CH3CH2

CH3CH2

(R)

CH3CH2

H
C

CH3CH2
H

Br

Br
C
(R)

C
(S)

,
, .

2--3--3-

80:
Br
(CH3)2 C CH CH3
F

CH3

SbF5
. SO2; -800

CH3

Br
+
C

CH3

SbF6

80
,
.
,

:
+ 2Br2

Br
+
Br3

, ,
392

H
CH2CH3

,
D- L-

393

, .
, ,

.

. ,
-:
.

Cl-,

-,

.

- ,
.
:
C

+ Br - Br

C
+
Br

Br

, ,
- ,
:
C

+I-I

C
+
I

,
(I2 + I- =
I3-) - I3- - ,
:
R
R C
I

C R + I3I

R
R C
I
I

R
C R
I
I

393

R
C

C
R

+ I2 + I3 ( I5 )

394

- ,

- .
, -
- ,
:
C6H5

H
+ Br2
C
CH3

C
H

C6H5

CH3COOH

H
C

C6H5

+ Br2
C6H5

H
CH3

Br

E-1-

C6H5

Br

H
C6H5

Br

C
Br

CH3

(32%),
-

Br
C

C
Br

(68%),
-

CH3NO2

H
C

H + C6H5
Br
C6H5

(10%),
-

Br

C6H5

(90%),
-

,
,

:
Hal

Hal
C

C
Hal

+ Hal2

C
+
Hal

Solv

Solv
C

C
Hal

-
.

: ,
:
C6H5CH=CH2 + Br2

CH3OH

C6H5 CH CH2Br + C6H5 CHCH2Br

Br
O-CH3

394

395

, , ,
.
(-, - ), ..
:

HOH

+ Cl2

Cl

Cl
+

+ HCl

Cl

..

OH
H

HO

+ HCl
Cl

-2-

,
,
.
. ,


C(1) Hal C(2) Hal
C(2).
C(2) , ,
.

CH3
C=CH2 + Br2
CH3

HOH

CH3

H
H
..O
+

C
CH3

+
Br

H
O
+

CH2 Br

CH3 C

CH2Br Br

CH3

OH
CH3 C CH2Br + HBr
CH3 (73%)

N- (NBS)
() :

395

396

O
R CH=CH2 +

H2O; H3C S

NBr

O
CH3

O
NBS

O S

...
..O.

H3C S

R CH CH2
+
Br

CH3

CH3
CH3

HOH

R CH CH2Br +
OH

R CH CH2Br

NH + H3C S

O
CH3

,
,

,
:
O
C6H5CH=CH2 +

- H2O

NBr

200C

C6H5 CH CH2Br (76%)

OH

O
C6H5CH=CHCH3 +

NBr

- H2O

N-

C6H5 CH CH CH3 (92%)

OH Br

( ) 5:
O

NH + Br2

NaOH

NBr + NaBr + H2O

H2O; 50C

.


. , .
396

397

5.5, , ,
-, - .
(2,3-2) 106 -1.


.
5.5

-1

0,01
1,00

--2

63

--2

20

1,00
27
17,5

2- ()
2--2 ()
2,3--2

58

57

11000

13700

430000

190000

()

. 5.5 ,
- --2, ,
, .
.
,
, (
) ( -2) .
,
.
,
,
-.

397

398

,
.

. 0

2-3-

()

:
(CH3)2C=CH2

Cl2 (1 )

CH2=C CH2Cl + HCl

CH3

00C

.. , .
, 1
14, , ,
14

CH2Cl.

:
Cl
14

CH2
CH3 C
CH3

Cl2
00C

H 2C C

+14

CH2

- H+

CH2=C

CH2 Cl

CH3

CH3

14

Cl

.
.
:
CH3

H3C
C
H3C

C
CH3

CH3

H3C
+ Cl2

C
H3C

Cl

C
+
Cl

CH3

- H+

H 3C
C
H 2C

CH3
CH3 + HCl
Cl

398

399

(CH3)3C-CH=CH2 + Cl2

CH
.. 3
+
(CH3)2C CH CH2Cl

CH3NO2

+
(CH3)2 C CH CH2Cl
CH3

1,2-
CH3-

- H+

H2 C

CH3
C CH CH2Cl + (CH3)3C CH CH2Cl
CH3
Cl
(10%)
(90%)

(. . 26). ,
,
, .
, :
Ph

H
C

Cl2

Ph

+
C

Cl

Cl

Cl

H
H

C-C

Ph

Cl

Ph C
H

H
H

Cl
+
C

H
C

H
Cl

Cl

Ph C
H

H
Cl

,

:
.
(,
),
.

, ,
,
, ,

399

400

.

,
:
RCH=CH2 + I+Cl-

RCH

+
I

CH2 + Cl

RCH CH2I
Cl

5.4.3..
()

.
HCl, HBr HI
:
(CH3)2C=CH2 + HCl
+ HBr
CH3

(CH3)3CCl (94%)

CH3COOH

CH3 (91%)
Br

CH3(CH2)2CH=CH2 + KI + H3PO4

CH3COOH

CH3CH2CH2CH CH3 (93%)

I

.
,
.
:
R2C=CHR R2C=CH2 > RCH=CHR RCH=CH2
,
,
: >>
>> (. . 9, . 9.3). ,
,
, .
.

400

401

,
,
. , , ,
,
: 1) -, 2) -
--.
,
,

1,2-,

,
-

1,2-

--2,

-3 . ,

- ,
- .
.
, ,
, .. AdE3-:
v = k[][HX]2
-

, :
H X ()
C

+ 2HX

H X
()

H
C

C + HX

AdE3 ,
HHal,
- -:
401

402

Cl

HCl

Cl
H

Cl

+
C

AdE 2

C
Cl
AdE 3

H
C

Cl
-

HX
. ,
,
.
-

, ,
.
-. ,

-, NR4+X-
. -.
,

--

:
H

Br
+ H
D
H

DBr

Br
H
D
H
-

- -
-

1-,

1--4-,

, .
,
,
(. . 9).

402

403

k[][HX],

..

AdE2-,
, -:
X

+
ArCH-CH2-R

ArCH=CHR + HX

ArCH CH2 R

, -
.
-, - HX.

Z-C5H5-CH=CH2.

, -
,
.
, AdE2-,

,
:
C6H5CH=CH2 + HCl

CH3COOH

C6H5CHCH3 + C6H5CHCH3
OCOCH3
Cl
(86%)
(14%)

1,2-
- :

403

404

(CH3)3C-CH=CH2 + HCl

CH3
+
CH3
CH CH3

CH3NO2

CH3

+
(CH3)2C CH CH3
CH3

Cl

(CH3)2C CH CH3
Cl CH3
(83%)

Cl

Cl
(CH3)3C CH CH3
(17%)

+
(CH3)2C CH CH3

(CH3)2CH-CH=CH2 + HCl

+
(CH3)2C CH2 CH3

Cl

Cl
(CH3)2C CH CH3
(40%)

Cl

(CH3)2C CH2 CH3

Cl
(60%)

.

.
([2.2.1]--2):
D
D
+ DCl

(57%)

+
Cl
Cl

D
+
Cl
(41%)

(2%)

DCl -;

. -
.

404

405

- ,

,
.
,

,
.

. (. . 11).
5.4.3.. .

(HBr, ICl, H2O, Hg(OAc)2

..) , ,
,
:
CH3CH2CH2Br
-
CH3CH=CH2 + HBr
CH3CHBrCH3
-

1870 . .. ,
HX ,
, H
, X .

. ,
,

. , ,

405

406

.

HX ,
. ,
HCl CF3CH=CH2 -
CF3CH2CH2Cl. , CF3CH+CH3
, CF3CH2CH2+ - (-I)- CF3-.

CF3CH2CH2+,

CF3,
HCl ,
.

HBr :
+
R3N-CH=CH2 + HBr

CH2=CH-Cl

+
R3N-CH2-CH2Br

, , HCl
1,1- (-) CH3CHCl2. , CF3, (-I)-, ,
,
+CH2CH2Cl , CH3CH+Cl.
CF3-
(+M)- ( ).
, ,
1- , (+M)-
:
+
CH2-CH2

Cl

2-
( )
(+M)-

CH2=CH-Cl + HCl

..
+
CH3-CH
Cl
-

1-
( )

406

407

, , ..
, 1 , C2H5+.

(. . 13).
HX , (-M)-,
CH2=CH-CN,
.
,
.

,
, ,
. ,
1--2, 2--1-:
CH3CH=CH2

Br2
HOAc

CH3 CH CH2Br + CH3CHBrCH2Br

OAc

, :

Br
+

CH3 CH

Br
CH3 CH

CH2

AcO

CH2
OAc

5.4.3..

407

408

, .

.

.
- (+M)- x (-M)- z. X
, R2N, RO, Hal , Z
COR, COOR, NO2, CN ..
HX - ,
1s-
- .
(. . 2, . 2.3): 1)
C = C -
x-CH=CH2 z-CH=CH2, 2)
sp2- . .

x
z , p-
C = C - x-CH=CH2 z-CH=CH2.
, , x=CH2-, z=CH2+. :
x-CH=CH2
.-.
CH2 CH CH2
z-CH=CH2
+
CH2 CH CH2
-
(. . 2, . 2.4).
:

408

409

1/2

1/2

1/2

1/2

1/2

1/2

- -CH2-CH=CH2

1/2

1/2

- +CH2-CH=CH2
1

(+ -)

x ( ) z ( ),
C .
,
,
CH2-,
. , ,
,
.
- C(2) C(3)
.
(
) -:
2

1
1
- C (2): + 0 =
2

2
2

- C (3):

2
3
1 1
=
+

4
2
2

,
.
-
-. ,
-.

409

410

, .. x-CH=CH2 z-CH=CH2.

x- -

x- -

z--

, (..
) - . . ,

, x-CH=CH2
. xCH=CH2 , , ..
. - x (..
(+M)-)
. , , ..
, (+M)
(+M)-.
z-CH=CH2
.
,
.
,

HX

,

.

5.4.3..

410

411

, ,
:
HOH
+
+
RCH=CH2 + H3O
[RCHCH3]

R2C=CH2 + H3O

+
[R2CCH3]

HOH

+
R CH CH3 + H
OH
+
R2C CH3 + H
OH

:
CH3CH2CH2CH2-CH=CH2 + H2O

HCOOH, HClO4
85-1000C, 3

CH3CH2CH2CH2 CHCH3 + CH3CH2CH2CHCH2CH3

OH
OH
(66%)
(34%)

:
65%- H2SO4

(CH3)2C=CH2 + H2O

CH3 + H2O

10 - 200C

60%- H2SO4

CH3)2C-OH
(45%)
CH3
OH
(40%)

0 -100C

(. 28):
CH2=CH2 + H2O

H3PO4/SiO2

CH3CH2OH
(95%)

3000C, 70

CH3CH=CH2 + H2O

H3PO4/SiO2
2500C, 40

CH3CHCH3
OH
(95%)

,
.

411

412

5.4.3..

, (II).
20
()
.

, ..
:
RCH=CH2 + Hg(OAc)2

- H2O
200C

R CH CH2-HgOAc
OH

-1
,
. C Hg
NaBH4
C H. ,
,
:
R CHCH2HgOAc + NaBH4
OH

R CHCH2HgH
OH

R CH CH3 + Hg
OH

,
.
,
90 98%,
:

412

413

1) Hg(OAc)2; - H2O; 200C

CH3(CH2)3CH=CH2

C6H5 C=CH2
CH3

CH3(CH2)3 CHCH3 + CH3(CH2)3CH2CH2OH

OH
(99,5%)
(0,5%)

2) NaBH4; H2O

OH
C6H5 C-CH3
CH3
(100%)

1) Hg(OAc)2; - H2O; 200C

2) NaBH4; H2O

(CH3)3C-CH=CH2

1) Hg(OAc)2; - H2O; 200C

2) NaBH4; H2O

(CH3)3C CHCH3 + (CH3)3CCH2CH2OH

OH
(97%)
(3%)

1) Hg(OAc)2; - H2O; 200C

OH

2) NaBH4; H2O

20

:
H3 C

H
C

+ Hg(OCOCF3)2

FSO3H - SbF5

CH3

H 3C

H
C

C
CH3
+
HgOCOCF3

, : ,
, .
, N-
, :
1) Hg(OAc)2; - CH3OH; 200C

CH3(CH2)3CH=CH2

2) NaBH4; CH3OH

1) Hg(NO3)2; CH3CN

CH3(CH2)3CH=CH2

2) NaBH4; CH3CN

CH3(CH2)3 CHCH3
O-CH3
(90%)

CH3(CH2)3 CHCH3
O-CH3
(92%)

. ,

413

414

.
, -,
AcOHg+
( ),

C(2):
+
RCH=CH2 + HgOAc

RCH
+
Hg

CH2

H2O

+
R CH CH2HgOAc + H
OH

OAc

Hg(OCOCF3)2
Hg(OSO2CF3)2:
1) Hg(OCOCF3)2; CH3CH(OH)CH3
2) NaBH4

O CHCH3
CH3
(98%)

,
.

().

. ,
, -.
,
.

5.4.3..

414

415

) RSCl RSBr

AdE-

,
, ,
RSCl RSBr

RS-

(1-):
R'CH=CH2 + R"SCl

R' CHCH2Cl
SR"

:
CHCl3

(CH3)2CHCH2CH=CH2 + -NO2C6H4SCl

(CH3)2CHCH2 CHCH2Cl + (CH3)2CHCH2 CHCH2SC6H4NO2 -

Cl
SC6H4NO2 -
(63%)

(37%)

, ,
.

:
Cl
C

C + RSCl

Cl

+
S

SR

AdE-,
,
, ,

.. .. . ,

415

416

RS+BF4- RS+SbF6-
,
,
, , , , .
, ..
Nu: :
+
R'2C=CH2 + R"S

R'2C

Nu..

CH2

R'2C CH2SR"
Nu

+
S-R"

RSCl -
,

(CH3)3CCH(SR)CH2Cl.

RS+BF4- - 1,2-
,
, , . RSCl RSBr

-2,

-3

40 +150,
RS+ +20 ,
- - :
CH3
C
+ ArSCl
H

H3C
C
H

Cl
-400-(+1500)C

CH3 CH CH CH3
SAr

CH3COOH

CH3

H3C
C

C
H

H
+
S-Ar

ArS +
-300C

CH3

H3C
C

ArS +
+200C

Nu:

CH3

H3C
C
H

H
+
S-Ar

H3C
C

C
H

CH3
+
S-Ar

Nu:

CH3 CH CH CH3
SAr Nu
-

CH3 CH CH CH3
SAr Nu
- (>95%)

Nu:

CH3 CH CH CH3
SAr Nu
-

LiClO4
(,
,

),

RS+.
416

417

. , SR+X-


.
(RS+), (RSCl)
..

..

, :
C

+
RS

RSCl

C
Cl

C
S

Y:

+
S-R
=
Cl

+
S-R
Cl

C
+
S-R

+
S-R
=
Y

, ,

SN 1- (. 9).
RS+
,
. ,
,

, R2PCl, RSeCl .
, -
(CCl4, CHCl3)
,

417

418

, -
Haln, n=4,6 .

,
.

5.4.3.

. Br+N3- I+N3-,
I+ - N3- = C = O, , Cl- N+ = O,
C6H5I(OAc)2

RSeCl.

IN3,

BrN3,

INCO

, -, -
-,

.
IN3, BrN3 INCO ,
- -
B2H6 .

0 10:
C6H5CH=CH2

1) B2H6,

AgN3 + I2
(0-10)0C,

C6H5 CH CH2I
NH2. HCl

2) HCl

IN3

C6H5 CH CH2I
+ N=N=N
(70%)

(50%)

,
-.

--

418

419

:
H

CH3
C

AgN3 + I2

H3C

N3
H
H3C

I-N=C=O.

CH3
C

H
I

H
N

LiAlH4

H3C

CH3
C

2-

,
(. 21). 2
.
():
AgNCO + I2

..

00

I-N=C=O + AgI

..

+ I-N=C=O

; 00

..

CH3OH

N=C=O

I
O
..
N C O-CH3
H

NaOH

O
..
N C O-CH3

H2O; 200C; 2

N C O-CH3

O
N C OH

NaOH
H2O; 1000C

NH + CO2
(90%) 2,3-

RSeCl

(. 5.4.3.).

419

420

, ,
-

,

:
+ NOCl

CHCl3

0-50C

Cl

N=O
H

; H 2O
O

NOH
Cl

Cl

.
NOCl
-.

-.

. , ,
SO2

-.

5.4.4.

,
. Y
X+ - Y- Y- = BF4-; SbF6-;
ClO4-; FSO3-.
, , RSCl RS+BF4 RS+SbF6- (. ) (CH3COO)2Hg
(CF3COO)2Hg (CF3SO3)2Hg.
.

420

421

,
(.. , .. ., 1982).
SO3 ,

XY+:SO2O-

OSO2Y,

X Y
:
XY+:SO2O

X +- Y + SO3

X +- O - SO2Y

X+ - O- X O SO2 Y , X+ Y-, ,
X Y, :
O
Cl2 + SO3

-780C
CH2Cl2

Cl-O S Cl
O
-780C

ClOC2H5 + SO3

CH2Cl2

Cl-O S OC2H5
O

R2NCl + SO3

R2N S OCl
O
O

R-S-S-Rl + SO3

RS S O-SR
O

SR

:
+

Cl -O -SO2Cl +

Cl
-780C
CH2Cl2

+
Cl -O -SO2OC2H5 + - C4H9CH=CH2

OSO2Cl
-600C
CH2Cl2

-C4H9 CHCH2Cl + -C4H9 CHCH2OSO2OC2H5

Cl
OSO2OC2H5
(56%)
(15%)

N,N- R2NCl RSSR

(. ),
SO3
:

421

422
- C4H9CH=CH2 + (C2H5)2N-Cl + SO3

CH2Cl2

-C4H9 CHCH2Cl
(88%)
OSO2N(C2H5)2
Cl

N-Cl + SO3

CH2Cl2

-C5H11CH=CH2 + C6H5S-SC6H5 + SO3

+ C6H5S-SC6H5 + SO3

(90%)

OSO2 N
-780C
CH2Cl2 - CH3CN

-780C
CH2Cl2 - CH3CN

-C5H11 CH-CH2-SC6H5
NH C CH3
O
SC6H5
NHC(O)CH3

SC6H5
C6H5S-N(C2H5)2 + SO3 +

CH2Cl2

OSO2-N(C2H5)2

5.4.5.

5.4.5.. HBr,
,

HF, HCl HI.
HBr
,
. 1933 .
,
HBr .
. ,
, (2) 1,2- 1,3 1,3-:
BrCH2CH=CH2 + HBr

BrCH2CH2CH2Br + CH3 CH-CH2Br

Br

. . 1933 .
422

423

,
.
, ,
O
C

O
C

- (CH3)3C O OH, H2O2 ..,

,
,
:
RCH=CH2 + HBr

RCH2CH2Br

,
,

,
:
:
O
C

O
C

.
O

O
C

h t

O
C
+ HBr

OH

O
C
2

+ Br

:
.
.
Br + RCH=CH2
RCHCH2Br + H, H = - 9 /
.
.
RCHCH2Br + HBr

RCH2CH2Br + Br + H, H = - 7 /

Br
, ,
.
C6H5COOH Br , C6H5COOBr H,
O H O Br,
, , C6H5COOH Br

423

424

.
, .

.
(. 4).
RCHCH2Br,
RCHBrCH2.

RCH2CH2Br. , ,
,
:
HBr; h

CH2=CH(CH2)8COOH

BrCH2CH2(CH2)8COOH

HBr, HCl, HI HF. C I

, I
:
RCH=CH2 + I

RCHCH2I + H, H = + 5 /

:
.

RCHCH2I + HI

RCH2CH2I + I + H, H = - 24 /

HCl HF ,
, ,
HCl (103,2 /):

RCH=CH2 + Cl

RCHCH2Cl + HCl

RCHCH2Cl + H, H = - 22 /

RCH2CH2Cl + Cl + H, H = + 8 /

, .

HF, HBr HI .

424

425

,
HBr .
, , ,
, CBrCl3:
CH3CH2H=CH2 + H2S

h
00C

CH3CH2CH2CH2SH + CH3CH2CH2CH2S-CH2CH2CH2CH3
(68%)
(12%)
1000C; O2

(CH3)2C=CH2 + Ch3CH2SH
CH3CH=CH2 + CF3S-S-CF3

(CH3)2CH2-S-CH2CH3
(94%)

CH3S CHCH2-S-CF3
CH3

(100%)

CCl4 CBr4 ,
, 1:1.
CH3(CH2)5CH=CH2 + CCl4
CH3(CH2)5CH=CH2 + CBr4

h
750

CH3(CH2)5CHClCH2CCl3
CH3(CH2)5CHBrCH2CBr3

ROOH
2RO
.
.
RO + BrCBr3
ROBr + CBr3
.
.CBr + CH (CH ) CH=CH
CH3(CH2)5-CHCH2-CBr3
3
3.
2 5
2
.
CH3(CH2)5-CHCH2-CBr3 + CBr4
CH3(CH2)5-CHBr-CH2-CBr3 + CBr3

, ,
,

:
.CCl + CH =CH
3
2
2

Cl3CCH2CH2

Cl3CCH2CH2CH2CH2

CH2=CH2

Cl3C(CH2CH2)n+2CH2CH2

nCH2=CH2 + CCl4

CH2=CH2

Cl3CCH2CH2CH2CH2CH2CH2

n(CH2=CH2)

CCl4

Cl3C(CH2CH2)n+2CH2CH2Cl + CCl3 ..

H2O

1100C;

Cl(CH2CH2)nCCl3

n = 1 (9%); n = 2 (57%); n = 3 (24%)

, n < 5
.

425

426

5.4.5.. N .

1942 . .
, N-
CCl4, ,
(
- ). N-
(NBS) ( )
:
O

O
NaOH

NH + Br2

NBr + NaBr + H2O

H2O; 50C

NBS
:
Br
+ NBS

(PhCOO)2

CCl4; 800C

NH

(85%)

O
O

CH3(CH2)4CH2CH=CH2 + NBS

C6H5CH=CH-CH3 + NBS
-

CCl4; 800C

CCl4

CH3(CH2)4 CHCH=CH2 + CH3(CH2)4CH=CHCH2Br +

Br
(17%)
(45%) : = 1:1

C6H5CH=CHCH2Br
(75%)
-

-1 ,
?
-.
NBS
.
,
NBS HBr,
NBS:
426

NH
O

427

HBr + (CH2CO)2NBr
Br2

h t

Br2 + (CH2CO)2NH

.
2Br

.
.

Br + R-CH2-CH=CH2

HBr + RCH-CH=CH2

R-CH-CH=CH2 + Br2

R-CHBr-CH=CH2 + Br ..

, (. 4).

C H- C H .
4, 4:
()
95 /

H ()

98 /
108 /

() H

H
()

87 /

,
~8 /, 11 /
20 / .
, ,
.

(. 7):
Br
+

(CH3)3C- O K

(CH3)3COH; 1000C

1,3-

N- N-,
. ,

400 500 (.. , 184 .):
CH3CH=CH2 + Cl2

400 - 5000C

ClCH2CH=CH2 + HCl

427

428

,
.

:
Cl2

2Cl.

CH2=CHCH3 + Cl

HCl + CH2=CH-CH2

CH2=CHCH2Cl + Cl ..

CH2=CHCH2 + Cl2

CH CH2Cl

H2C
O

.
,
, ,
,
.

5.4.6.

: 1) , , 2)
.
, ,
- -.
,

.
.

5.4.6..

428

429

()
O
O OH

RC

,
, .
RCH=CH2 + R'C

O OH

()

R CH

CH2Cl2

CH2 + R'COOH

()

,
.
,
,
OH+.
-
:
H
C

+
R' Cl

H
C

CH2Cl2

H
+

R'

Cl

COOH

Cl

COOH

O OH
-

R
C

+
R' Cl

H
O

CH2Cl2

H
+

R'

O OH

,
(. . 25):
R'
R'
C
H

R"
C + R'"COOOH
H

R'

-,
429

H
C

C
H

R'"

O
O

R"

H
C

O +
C
R"
H

R'"
C
OH

:
,

430

.
,
CH3CO3H, CF3CO3H HCO3H

30- 90%- .
-
-
70%- :
O
COOH
+ H2 O2

O-OH
CH3SO3H; 250C

+ H2 O

:
O

O
Cl

+ H2 O2

Cl

O-OH

MgSO4
NaOH; H2O-

+ H2O + NaCl

Cl

30%- :
O

O
O + H2O2

O-OH

1) NaOH-H2O; -5-(-10)0C
2) 20%- H2SO4; 00C

OH
O

()
:

430

431
O

CHCl3

C6H5CH=CH2 + C6H5COOOH

C6H5 CH CH2 + C6H5COOH

(75%)

00C

CH3

H3C
H3C
O
C

CH3

H3C
O-OH

COOH

O
O C
CH3

CH3

H3C
H3C

CH3

H3C

COOH
+

O
O C
CH3

(87%)

COOH

.
,
( ) ,

.
.
( 1 )
. ,
-
, .

431

432
CO3H

COOH

CH2Cl2

00C

(80%)

Cl
CO3H

CH3(CH2)5CH=CH2 +

Cl
O

CHCl3
00C

(90%)

Cl
H3 C

CO3H

H
C

COOH
CH2 +

CH3(CH2)5 CH

CH2Cl2; t

Cl

H3 C
C

+
COOC2H5

COOC2H5

(70%)

Cl

COOH

Cl

90%-
:
CH3(CH2)5CH=CH2 + H2O2 + CH3COOH
(90%- )
C6H5

CH2Cl2

H
C

+ H2O2 + CH3COOH
C6H5 (90%- )

O
CH3(CH2)5 CH
(80%)

CH2Cl2

C6H5
C

H
C

CH2 + H2O + CH3COOH

+ H2O + CH3COOH
C6H5

O
CF3CO3H
CH2Cl2

(87%)

, ,
,
,
90%- .

90%- :

432

433
NH
RC N + H2O2

R C
O-OH

NH
R C
O-OH

+ R'CH=CH2

R' CH

CH2 + R C

NH2

:
CH2=CH2 + O2

Ag
250 -

H2 C

3000C

CH2
O

.
11,
. .
, .
, .. .

O
C

C + H+

H
O+
C

HOH

H
O
C

H
O
C

O
H + H

..

, ,
.

-
.

, -
-1,2-:

433

H
O
C

C
O
H

+ H+

434

H
H
.O.
H
+
OH

O
H

OH

+ H+

(86%) OH
-1,2-

,

- .
- ,
30 70%-
.
, ,
- , :
OH

CF3CO3H - H2O2

(82%)

CH2Cl2

z-CH3(CH2)7CH=CH(CH2)7COOH

OH
30%- H2O2
HCOOH; t

OH OH
CH3(CH2)7 CH CH (CH2)7COOH (80%)
-9,10-
-9,10-

, ,
-:
H

:OH

OH

O
H

HOH

OH

H
OH
-1,2-

,
.
-
. (1933 .).
CCl4.
, -,

434

435

:
RCH=CH2 + I2 + C6H5COOAg

C6H5COO

R CH CH2 I

R CH CH
+
I
C6H5COO

R CH CH2 O
O

O
C 6 H5

C 6 H5

C6 H 5

,
:
z-CH3(CH2)7CH=CH(CH2)7COOH

OH OH
CH3(CH2)7 CH CH (CH2)7COOH (75%)
-9,10-
-9,10-

1) I2-C6H5COOAg; ; 800C
2) NaoH - HOH

H
I2-C6H5COOAg; ; 800C

O
C6H5

O
O

-1,2-

C6H5
O

H
(44%)

,
- .

-
.

-1,2-

.. 1878 .

0:
OH

KMnO4
H2O; 0-50C; pH=7,5-8

(37%)

+ MnO2 + KOH
OH

., , -

435

436

.
,
, .
,

(pH ~ 8)
0 5 ~ 1% KMnO4.
(30 60%):
CH3
OH
CH3 (45%)
-; 0-100
CH3
OH
-1,2--1,2

CH3

KMnO4

KMnO

4
ClCH2 CH-CH=CH2
-; 0-100
Cl

z-CH3(CH2)7CH=CH(CH2)7COOH

ClCH2 CH CH-CH2OH
(56%)
Cl OH
KMnO4

; 0-100; pH=8

OH OH
CH3(CH2)7 CH CH (CH2)7COOH (81%)
-9,10-
-9,10-

,
:
R'
R'
C
H

R"
C + KMnO4
H

R"
C

C
O

Mn
O

HOH

R'
C
H

OH

R"
+ MnO2 + KOH
H
OH
C

OK

, 18O
. . (1957 .) ,

KMn18O4. , ,
,
.

436

437

-
(VIII) OsO4 . 1936 .
,
, , .

,
. OsO4
.

:
R"

R'
R'
C
H

C
C
R"
R'

H
H NaHSO3 - H2O
C + OsO4
O
O
C

H2S
H
Os
H OH
O
O

OH H

HO

R"
C

Os
HO

-
, .

,
:
O
CH3

Os O

H3C O
CH3

+ OsO4

1) OsO4 -
2) NaHSO4 - H2O

NaHSO3

H3C OH
OH
-H O
2

CH3

CH3

(87%)

OH
(98%)
OH
HO

1) OsO4 -

OH
(98%)

2) NaHSO4 - H2O

,
. (VIII)

. -

437

438

OsO4

.
OsO4, :
H
+ H2O2

OH
(58%)
OH

OsO4
00C

,
(V2O5, WO3, MoO3 .) - .
. 1958 .
- . -

.
.
:
H
1) I2; CH3COOAg
2) CH3COOH + H2O
3)

OH
OH

(66%)

- -
, - -, -, - d-,l-,
:
-

-, -
-

-, -
d-,l-

- - , , ,
, .

438

439

5.4.6..

KMnO4 ,
(VI) CrO3

.

()
.
,
,
.

:
KMnO4

R'CH=CHR"

RCH=CH2
R

R'COOH + R"COOH

H2SO4 + H2O
K2Cr2O7
H2SO4 + H2O

RCOOH + CO2

KMnO4

H2SO4 + H2O

O + O

.
,
*.
.

(. . 12)
80 95%,
.

439

440

5.4.6..

.

,
.
5 10%-
80 (-100).
.

. 1950 1956 . 1,3-

(1,2,3-).

(1,2,4-):
..

O
..
C

..
..O
..

..O

..O
..

O..
..

...O.

O..
.. ..
..O

.
O
...

(1,2,4-)

(1,2,3-)

,
.
1,2,3-

(), 1,3 (. . 25):
R"

R'
C
H

.
O
... ..
..O

.
O
...

. ..
O.

R'

C
O
..

440

..
R"
..O
..

..

O
..

C
R'

...O.

H
C

.
O
...

R"

441

,

,
. , , -
,

18

O, ,

:
O

O3, CH2Cl2;

- 80 0C

18

C6H5CH=CHC6H5 + C6H5C

18

C6H5CH
O

H
C
C6H5
O

:
H

O C

18

C6H5CH

18O
H
H
C
C
C6H5
C6H5
O O

C6H5
O

,
, , ,
, - .

, :
+ R2C=O-O + CH3OH

R2 C O-CH3
O-OH

C6H5=CH2 + O3

CH2Cl2
-780C

O-CH3
O
+ CH2O
C6H5 CH O-CH3 + CH2 O-OH + C6H5 C
H
O-OH
(31%)
(23%)
(26%)
(27%)

,
-
,
.

. , ,

441

442

.
.
.

:
R1
H

O O
O

R2
C + HOH
R3

R1C

+ R2C

R1

R3

O O

HO

H O

+ H2O2

R2

R1

R3

H
O

R1C

R2
O OH
+ O C
OH
R3

+ R2C

OH

O
R3

. ,
.

:
1) -C6H5CH=CH2

+ O
O
+ CH3 S
+ H C
CH3
H
H
(73%)

1) O3 CH3OH; -780C

- C6H13 C

2) CH3-S-CH3

1) O3; CH2Cl2; -780C

2) H C
3

CH=CH2

CH3CH2

2) Na2SO3 - HOH

CH3

3)

1) O3; CH2Cl2; -780C

2) Zn - CH3COOH

H3 C
CH3

2) H2 / Pt

CH3

CH3CH2 C
(90%)

O
CH3

+ CH3CHO

CH3 O

CH2
1) O3 CH3OH; -780C

5)

N
(80%)

O
H3C C (CH2)4CHO
(85%)

1) O3; CH2Cl2; -780C

4)

H 3C

H C

+
CHO

+ HCHO

2) CH3-S-CH3

(76%)

:
1

O O
O

H
H
3
O
O
R
R
C 4
2 C
R
R
O
1

[H]

442

C O +

C O + H2O

443

,
,
.
,
:
CH3(CH2)7CH=CH(CH2)7COOCH3
CH3(CH2)7CHO +
(79%)
C

CH3

1) O3, CH2Cl2, - 780C

CH3

2) Zn - CH3COOH - H2O

1) O3, CH2Cl2, - 780C

2). Zn + CH3COOH

H(O)C(CH2)7COOCH3

O + O=C(CH3)2
(84%)

,
.
,
:
CH3CH2CH2

H
C

1) O3; CH2Cl2; -780C

C
CH2CH2CH3

H
1) O3; CH2Cl2; -780C
2) NaBH4; CH3OH

2) NaBH4; CH3OH

CH3CH2CH2-CH2-OH
(95%)

HOCH2(CH2)4CH2OH
(63%)

CH3CH=CH(CH2)7COOCH3

1) O3; CH2Cl2; -780C

2) NaBH4; CH3OH

CH3CH2OH + HOCH2(CH2)7COOCH3
(91%)

, ,
.

,
.

1955 . . .

NaIO4
pH ~ 7 8. .

443

444

,
.
,
.

:
R'CH=CHR"

KMnO4
NaIO4; 5 - 100C

R'COOH + R"COOH

pH~78 -

- -

CH2
CH3
CH3

KMnO4
NaIO4; 0-50C
-

+ HCOOH
CH3
CH3

, ,
, -
5 10 6--4-
:
H3 C

H2C

CH2

H2C

CH2OH

KMnO4

H2C

CH2

NaIO4; 0-50C
-

H2C

CH2OH

(100%)

C OH

C
H3 C

H3 C

CH3

(
) . ,
- :
CH3(CH2)5 CH CH2CH=CH-(CH2)5CH2OH
O-COCH3

KMnO4 - KIO4 - K2CO3

- -

CH3(CH2)5 CH CH2-COOH + HOOC-(CH2)5CH2OH

O-COCH3
(92%)

(, ,
444

445

1956). OsO4 NaIO4 ,

.

:
2

R1CH=CR2R3

OsO4

R CH C
O

O
Os

NaIO4

O
O
2
1
R C + R C 3 + OsO4 + NaIO4
R
H

RuO4.
, :
1) OsO4 -

O
H

2) NaIO4 -

(77%)

O
CH3(CH2)9CH=CH2

1) OsO4 -
2) NaIO4 - ; 250C

CH3(CH2)9CHO (68%)

, ,
, OsO4 NaIO4

.
-
.

5.4.7.
. , 1959 .,

,
: , ,
.

445

446

. , BH3,
.
.
. ,
. B2H6
B H
B.
H

H
H

H
B

,
.
-
. - B2H6
, - C2H6, 2 .
B2H6

C2H6 BH3 CH3

. ,
-,
-:

BH3 B B
, BH3
:

2BH3 = B2H6 ,
.

BH3

B H. ,
BH3 B2H6 -,

446

447

CH3, ,
- B H :
..
B

H
+
H

..

BHB ,
.
( ),
, .
: B5H9, B6H10 ,
,
, ,
.

( ).

3NaBH4 + 4BF3. (C2H5)2O

2B2H6 + 3NaBF4 + 4(C2H5)2O

-
:
B2H6 + 2

2 H3B

BH3,
:
3 RCH=CH2 + BH3

(RCH2CH2)3B

.
:
RCH=CH2 + BH3

RCH2CH2BH2

B H,
:

447

448

RCH=CH2,

RCH2CH2BH2

RCH=CH2,

(RCH2CH2)2BH

(RCH2CH2)3B

,
.

-

.
C B C H .
:

+ H

H
H

BH2

- p-
. C B
B H:

BH3
,

(2,0) (2,2),
B H . ,
p-,
.
.
. ,
,
448

449

, -

-(3--2-)-,
BH3 3--2:
2 (CH3)2C=CHCH3 + BH3

(CH3)2CHCH

BH
2

CH3

(Sia)2BH.
1:1 2,3--2, :
CH3
(CH3)2C=C(CH3)2 + BH3

(CH3)2CHC

BH2

CH3

1-
BD3:
CH3 + BD3

D
CH3

B
3

, , ,
.

.

:
+

R3B + 3 HX

3 RH + BX3

449

450

(H2SO4, HCl, HBr .),

RCOOH
:
(RCH2CH2)3

O
B + 3 CH3C
OH

CH CH R
RCH2CH2 B CH2 CH2 R
2
2
3
H
O
O C CH
3

3 RCH2CH3 + (CH3COO)3B

,
.
CH3COOD.

.


.
C B
.

:
RCH=CH2

BH3

H2O2

(RCH2CH2)3B

H2O2
NaOH-H2O

RCH2CH2OH + NaB(OH)4

. , , 1
-2-.
, BR2
.

450

451

(. 5.4.3.). , ..

).

80 95%:
1) BH3 -

RCH=CH2

R2C=CH2

RCH2CH2OH
2) H2O2 - NaOH
1) BH3 -

2) H2O2 - NaOH

R2CH-CH2OH

. -
:
R
R3B + : OOH

OOH

-.

B O
C B:
R
R

R
O

OH

OR + OH

2p-
2p- , B O. 1,2-
, ,

1,2-
(. . 9):
C

..

+
C

+
C

C
R

451

452

R2BOR

():
R2BOR + 2 OOH

(RO)3B + 2 OH

-:
3ROH + B(OH)4

B(OR)3 + OH + 3H2O

BH3
,
90%.
:
CH3(CH2)3CH=CH2

1) BH3 -
2) H2O2 - NaOH - H2O

C6H5CH=CH2

1) BH3 -
2) H2O2 - NaOH - H2O

CH3CH2C=CH2

1) BH3 -
2) H2O2 - NaOH - H2O

CH3(CH2)4CH2OH + CH3(CH2)3CHCH3
(94%)
(6%) OH

C6H5CH2CH2OH + C6H5CHCH3
OH (20%)
(80%)
CH3CH2CHCH2OH + CH3CH2C(CH3)2

CH3

CH3

(CH3)2C=CHCH(CH3)2

1) BH3 -
2) H2O2 - NaOH - H2O

OH
(99%)

(1%)

(CH3)2CHCHCH(CH3)2 + (CH3)2CCH2CH(CH3)2
OH
OH
(98%)
(2%)

,

R2BH, -(2--2-)- (Sia)2BH:
CH3(CH2)3C=CH2

C6H5CH=CH2

1) (Sia)2BH -
2) H2O2 - NaOH - H2O

1) (Sia)2BH -
2) H2O2 - NaOH - H2O

CH3(CH2)4CH2OH + CH3(CH2)3CHCH3
OH
(99%)
(<1%)

C6H5CH2CH2OH + C6H5CHCH3
OH
(1%)
(99%)

452

453

. 20 100
, 2---1.

:
(Sia)2BH -

(Sia)2B

- 100 , , .

9--[3.3.1] (9-). ,
. 9-
.
1) 9-BBN; , 250C
2) H2O2-NaOH-H2O

CH3(CH2)3CH=CH2

-C3H7

CH3
C

C
H

CH3(CH2)4CH2OH + CH3(CH2)3CHCH3
OH
(99,9%)
(0,1%)

1) 9-BBN; , 250C
2) H2O2-NaOH-H2O

-C3H7-CH2CHCH3

(99,8%) OH

9-[3.3.1] BH3
--1,5- ( . . 7):
BH
+ BH3

, 650, 1

(99%)

, ,
.
.

:
R3B + 2 I2 + 2 NaOH

RB(OH)2 + 2 RI + 2 NaI

-RI .

:

453

454

1) BH3;
2) ICl

CH3(CH2)2CH=CH2

(100%)

1) BH3-
2) Br2-NaOCH3;

CH3(CH2)3CH2Br
(70%)

.
:
RCH=CH2

1) BH3-
2) Br2-NaOCH3;

RCH2CH2Br

-O-.

:
..

R3B + NH2X
R

+
N

R2 B N H
R

.. H H

OH

RNH2 + B(OH)4

x = Cl OSO3-

,
(. , . , 1967). p-
R3B 2s-
1:1:
R3B + : C

R3B

.
,
R3B--CO+,
100 120
, ,
:

454

455

R
R B C O
R

100-1250C

R3B + CO

R
B

R
O=B C

B C R
R
R

H2O2
NaOH-H2O R C OH + B(OH)4

:
BH3;

B
3

1) CO; 1000C
2) H2O2-NaOH-H2O

COH
3

(85%)
BH3;

CH3CH=CHCH3

1) CO; 1250C

CH3CH2CH 3B 2) H O -NaOH-H O
2 2
2
CH3

CH3CH2CH 3COH
(87%)
CH3

.
,
.
NaBH4 ,
:
R
R B C O
R

B C R
R

1) NaBH4
RCH2OH + 2 ROH + Na B(OH)4
2) H2O 2-NaOH-H2O

:
R
R B C O
R

1) NaBH4
2) H2O2-NaOH-H2O RC(O)R

R B

B C
R

OH
R
R B C
R
OH

R
R

2 ROH + Na B(OH)4

455

456

-5:
+ BH3

O
C

3B 1) CO, 1250C; H2O

2) H2O2-NaOH-H2O

(90%)

1) CO, 1250C; H O

BH3

(CH3CH2CH2CH2)3B 2) H O -NaOH-H2 O
2 2
2

CH3CH2CH=CH2

(CH3CH2CH2CH2)2C=O
-5 (90%)

. ,
(i=PrMe2C) :
(CH3)2CH-C(CH3)2BH2 + (CH3)2C=CH2
CH2=CH-CH2COOC2H5

(CH3)2CHC(CH3)2 B

(CH3)2CH-C(CH3)2 B

(CH3)2CHC(CH3)2-BHCH2-CH(CH3)2

CH2CH(CH3)2
CH2CH2-CH2-COOC2H5

CH2CH(CH3)2

OH OH

CO; H2O

CH2CH2-CH2-COOC2H5

H2O2
CH3COONa; H2O

O
(CH3)2CHCH2C
CH2CH2CH2COOC2H5
(84%)

- . 6.
5.4.8.

,

.
, .
; ,
, .
,
.

456

457

,
.
,

.
, ,
. ,

, ,
. ,
,
.

.
.
5.4.8..

, () .
(
, ), --(-)
(CH3)2C N N C(CH3)2
CN
CN

,
.

457

458
:
O
O
R C O O C R
:
R. + CH2=CHX

O
2 R C O.

R. + CO2

RCH2-CHX

RCH2CHX + CH2=CHX

RCH2-CHX-CH2-CHX

n CH2=CHX

2 RCH2CH (CH2 CH) CH2-CHX

n
X
X
RCH2CH (CH2 CH) CH2 CH
n
X
X
X

CH CH2 (CH CH2) CHCH2R

n
X
X
X

,
,
(. 4):
.

RCH2 CH (CH2 CH)n CH2 CH + R1H

X
X
X

R1 + RCH2 CH (CH2 CH)n CH2 CH2

X
X
X

2 RCH2 CH (CH2 CH)n CH2 CH

X
X
X
RCH2 CH (CH2 CH)n CH
X
X

CH + RCH2 CH (CH2 CH)n CH2 CH2

X
X
X
X

,
,
, , 10-8 /.

.
.


. , ,
,
; -
() ,
458

RCH2CH (CH2 CH) CH2-CHX

n
X
X

459

:
.

...-CH2 CH (CH2 CH)n CH2 CH + CH2=CHC6H5

C6H5
C6H5
C6H5
...-CH2

...-CH2 CH (CH2 CH)n+1CH2 CH

C6H5
C6H5
C6H5

CH3
CH3
CH3
CH3
.
C (CH2 CH)n CH2 C
+ CH2=C
COOCH3
COOCH3 COOCH3 COOCH3

...-CH2

CH3
CH3
CH3
C (CH2 CH)n+1CH2 C .
COOCH3 COOCH3 COOCH3

,
,
. ,
, , ,
,
.
, , , , ,
, .

.
. , ,
, ,
, ..
(II), .
:
2+

3+

Fe + HOOH

n-CF2=CF2
CH2=CHCN

Fe + OH- + HO
Fe2+; H2O2
H2O
FeSO4; H2O2
H2O

...-(CF2-CF2)n-...

...-(CH2 CH)-...
n
CN

,
. , ,

, ,
. ,
459

460

, ,
300.
, .

100 300 100 3000 .
.
, ,
110.
5.4.6..
.
,

.
. ,

.
, CH2=CH-OR, 3--1
.
: BF3, AlCl3, AlBr3
.
, :
:
H2O + BF3

H + BF3(OH)

H + CH2=C(CH3)2
CH3
+
CH3 C + CH2=C(CH3)2
CH3

CH3
CH3 C +
CH3

CH3
CH3
+
CH3 C CH2 C
CH3
CH3

CH3
CH3
+
CH3 C CH2 C + n CH2=C(CH3)2
CH3
CH3

CH3
CH3
CH3 C CH2 C
CH3
CH3

CH3
CH2 C+
CH3

( ). ,

460

461

, ,

.
, .
5.4.8..
CH2=CHX
(X=R; Cl; CN; COOR .)
,
:
*
*
*
*
...CH2 CH CH2 CH CH2 CH CH2 CH-...
X
X
X
X

n CH2=CH X

(. 8) ,
, X, .

X ,
, .
H

H
H

H H3C

CH3
H

H
CH3
H3C

CH3 H3C

CH3 H

CH3 H

H
CH3 H3C

CH3

H
CH3 H3C

H
H

H
CH3 H3C

(syndyo (.) - )

461

CH3

CH3

CH3

CH3

CH3

(taktikas (.) - )
H
H
H
H

CH3

CH3

CH3

H
H

CH3

CH3

CH3

H3C

CH3
H

462
H

H
H

H H3C

H H3C

H
H

CH3

H
H

CH3
H3C

H
H

CH3

CH3

CH3

CH3

H3C

H H3C

H H3C

H H3C

CH3
H

(iso (.) - )

X ,
R- S-
. CH2=CHX

.
X (, X = CH3)
.
,
: R, S, R, S, E, S, R, S ..

,
.
X . -
1953 ., .
.

,
,

-,
(R3Al)
TiCl4. -
. ,

, .

462

463

. ,
-,
175,
30. ,
, ;
.

.
. .
1963 . .

5.5.

R1 C: R2,
.
R - :N: .

,
- C H.
5.5.1.

:CH2, ,
.

,
.
, ,
.

463

464

, .
sp2- ,
sp2- (), p-
() . sp-
,
p-. H C H

102,

135 140.
. ,
10 /
:
-
H
C

sp2-

-
-
H

.
, :CHal2
, ,
. Cl C Cl
, 106, .

, -,
.
Cl
Cl

Cl

Cl

Cl
Cl

13,5 /.
5.5.2.

464

465

, .
(. 22).

CH2=N+=N-:. ,
:
h

CH2=N=N

N + CH2

:CH2
.

.
,
.

, ,

.
-

. , ,
,

(- , - .)
.
.

CH3OCH2CH2OCH3
()

CH2CH2OCH3 ():

465

CH3OCH2CH2-

466

R2
R1-C N-NH-Ts

O
R2 + NH2-NH-Ts

R1-C

-BH

R
R1
h
R1-C N N Ts
C + N N + Ts
0C

t
R2
R1C
2

SO2

Ts = CH3

( -))

,
-
. ,

(. , 1950).
C H pKa~16 (. 3).

CHal3 ,
- :
CHCl3 + (CH3)3CO

CHCl3 + OH

CCl3 + (CH3)3COH

CCl3 + H2O

CCl2 + Cl

CCl2 + Cl

. 120
:

CHCl3 + -C4H9Li -1000C

Cl3CLi + C4H10

-700C

CCl2 + LiCl + C4H10

, RLi,
1,1- :
. -1200

CH2Cl2
+ C4H9Li

-BuLi,

C6H5CHBr2
,-
()

- 780

- 780

-800

.. CHCl + LiCl

..

C6H5CBr + C4H10 + LiBr

-C4H9Li,

C6H5CH2Br

LiCHCl2 + C4H10

..

C6H5CH + C4H10 + LiBr

466

467

. :CH2
,
,
. .
LiCCl3, LiCHCl2, C6H5CH(Li)Br,
,
.
,
, .

.
,
, , ,
. ,
LiCCl3 :CCl2 , ,
.
,

C6H5CHBr2 -,

C6H5CH:.

:
Cl3C

Cl2C + Cl + CO2

Cl3C + CO2

:CHal2

C6H5HgCHal3 (. . 19).
-

:
C6H5HgCHal3

467

C6H5HgHal + ..CHal2

468

,
,

. ,
R3SnCHal3, R3GeCHal3 ., ,
C6H5HgCHal3.
5.5.3.

5.5.3..


.
1954 . ,

:
CHR2

R1CH
R1CH=CHR2 + CX2

C
X

.
, ,

, .
p-.

..

.
,
:

468

469

+ CHBr3

(CH3)3COK

Br
Br

(CH3)3C-OH; 00C

(80%)
7,7-

(CH3)2C=C(CH3)2 + CH2Cl2 + -C4H9Li

(CH3)2C

- 350

C(CH3)2

(67%)

CH
Cl

.
,
, .
(. . 25):
H

H
C

+ .. CX2

H
C

C
R

+ .. CX2

H
C

X
H

C
R

C
X

--2:
C2H5
H

CH3
H

+ CHCl3

C2H5

(CH3)3COK
(CH3)3COH; 0-100C

C
CCl2

CH3
H

(67%)

- (, , ,
)
.


( . 9).
,

(II),

469

470

, .
-
. CCl3- -
, .

:
NaOH + Q+Cl-

NaCl + Q+OH-

Q+OH-

Q+OH-

Q+OH- + CHCl3

H2O + Q+CCl3-
Q+Cl- + : CCl2

Q+CCl3-
R2C = CR2 + : CCl2
Q+Cl-

R2C
Q+Cl-

CR2
CCl2

Q+=N+(CH2C6H5)(CH2CH3)3; N+CH3(C8H17)3
.

.
(. , 1969)
.

. 1,1-
, , .

:

470

471

C6H5CH=CH2

CHCl3 - H2O - NaOH

N+(CH2C6H5)(CH2CH3)3Cl-

CHCl3 - H2O - NaOH

Cl

N+(CH3)(C8H17)3Cl-

Cl

CH3(CH2)3CH=CH2

(85%)

C6H5 CH CH2
C
Cl
Cl

CHCl3 - H2O - NaOH

(70%)

CH3(CH2)3 CH CH2

N+(CH3)(C8H17)3Cl-

Cl
H

CHCl3 - H2O - NaOH

N+(CH2C6H5)(CH2CH3)3Cl-

(60%)

Cl
(94%)

C
Cl

Cl

1,1-
- .

:
Cl
Cl

+ Li + (CH3)3COH

CH2

(86%)

(. 25)

(2 + 2)-.
2.4.1.. (. 2).


.
,
.
C C- .

. ,

:

471

472

R1
C
H

R2
H

+ CX2

R2
R2
R1
R1
C C
C C

H
H
H
H
CH2
CX2
;

--

R2
H
C C
R1
H
CH2

R1

R2

H
X

R2
H
C
C
R1
H
CH2

H
R1

R2
H
X

.
,
.


. 1958 .
. .
.
:CH2, IZnCH2I,
- :
CH2I2 + Zn(Cu)

ICH2ZnI

(ICH2)2Zn + ZnI2

ICH2ZnI ,
:CH2 ,
.

, 30 90%:
+ CH2I2

Zn(Cu),
400C

(92%)

[4,1,0]
()

472

473

Zn(Cu),

CH2=CHC(O)CH3 + CH2I2

CH2

400C

CHC(O)CH3
(50%)

CH2
Zn(Cu)

CH3(CH2)4CH=CH2 + CH2I2

, 400C

CH3(CH2)4 CH

CH2
CH2

(30%)

. , , --4
-
:
-C3H7
C
H

-C3H7
N2CHCOOC2H5
H
C
0
H
C3H7- CuSO4, 90 C

+ N2
C3H7-
(62%)
H COOC2H5
C

, .
,

,
, ,
:
H

COOC2H5

+ N2CHCOOC2H5

COOC2H5

+
h
2+
Cu

(31%)
(69%)

H
(16%)
(4%)

,
.
-1,3,5:

+ CH2N2

473

474

+ CHN2COOC2H5

CHCOOC2H5

COOC2H5

5.5.3.. C H

C H .
, C H
. C H ,
:CH2
. , , :CH2
- .

.
C H-
, C H-.

. C H.
C H,
:
CH3CH2CH3 + CH2

CH3CH2CH2 + CH3CHCH3 + CH3

5.5.4

R N:, .. ,
. ,
-
N3C-COOC2H5,
, :
- .. + .. O
.. N=N=N C OCH CH
2
3

N2 +

.. O
..N C OCH2CH3

474

O
N C OCH2CH3
(50%)

475

, ,

.
1,3- (. 25)
,
.
.
, :
. . .N.
N+

..

250

..

..N

C O
OCH2CH3

N ..

N
COOCH2CH3

N COOCH2CH3

+ N2

(95%)

,
, , ..
. 26.

475

476

6.

6.1.
6.2.

6.2.1. -

6.2.2.
6.2.3.
6.3.

6.3.1.
6.3.2.
6.3.3.
6.3.4.
6.3.4..
6.3.4..
6.3.4..
6.3.4..
6.3.4..
6.3.4..
6.3.5.
6.3.6.
6.3.7.
6.3.8.
6.3.9.
6.3.10.
,

.
. ()
1,203 :
1,601

1,203

180

476

477

- - .
,
sp- . -,
sp- s- (sp-s),
, sp2-s- - ,
. - : sp3-s > sp2-s > sp-s.
-
sp- : -. - pz
py . -
.
1.
. 6.1.
6.1

()

- 82

- 84

0,620

HCCH

80

CH3CCH

- 104

- 23

0,678
27

-1

CH3CH2CCH

- 130

0,67

-2

CH3CCCH3

- 28

27

0,69

-1

CH3CH2CCH

- 95

40

0,69

-2

CH3CH2CCCH3

- 101

55

0,71

3--1

(CH3)2CHCCH

28

0,67

-1

CH3(CH2)3CCH

- 124

71

0,73

-2

CH3CH2CH2CCH3

- 92

84

0,71

-3

CH3CH2CCCH2CH3

- 51

82

0,73

3,3--

(CH3)3CCCH

- 81

38

0,67

-1

CH3(CH2)4CCH

- 80

100

0,73

-1

CH3(CH2)5CCH

- 70

126

0,75

-1 (-)

477

478

-1

CH3(CH2)6CCH

- 65

151

0,76

-1

CH3(CH2)7CCH

- 40

182

0,77

-5

CH3(CH2)3CC(CH2)3CH3

78

25 Hg

6.1.
, ,
,
:
CH3CH2CCCH3

(CH3)CCCH

C6H5CCC6H5

, :
CH3CH2C

CCH3

CH3
CH3

-2

C C

CH

CH3
3,3--1
8

CH3CH2

CH2

CH C

C CH2CH3

CH2CH3
5--3

, , ,
., :
HO CH2

CH2CH2C

CH

H C

4--1-

CH2

CH C

CH

CH3

3--4-

,
:
HC

CH CH2

CH2

CH CH2

CH3CH CH C

1--5-

-3--1

478

CH3

479

6.2.
:
- ,
.
6.2.1.

-
70%. ,
,

(. 9),
-1:
RC1

+ R2CH2Br

R1CCCH2R2 + Br

, , pKa
25.

10%
2- (. 10).

.
, SN2-,
(. 9),
(), N-
. . .
6.2.
.
6.2

479

480
-

1) HC CH

NaNH2
NH3
- 33

2) CH3(CH2)3C

CH + -C4H9Li

NH3
- 33

-
- 25

CH3(CH2)3C C

-
25

3) 2HC

CH3(CH2)3I

HC C Na

HC CH2CH2CH2CH3 + NaI

CH3(CH2)3C C

Li

(CH2)4CH2 + LiBr

(90%)

, 25

C Na + BrCH2CH2Br

HC CCH2CH2C CH + 2NaBr
(81%)

4) HC

C Na + CH3(CH2)Br

1) NaNH2

CH3(CH2)3C

2) CH3(CH2)3Br, , 21

5) CH3(CH2)3C

-
25

C CH CH3 + CH3CH CH2 + CH3(CH2)3C CH

(94%)

CH3

Li + CH3CH2

CH CH2Br
CH3

CH3(CH2)3C

CCH2

(37%)

CH

(76%)

(6%)

H3CH2CH2CH2C

C(CH2)3CH3 + 2NaBr

Li + (CH3)2CHBr

CH3(CH2)3C

6) CH3(CH2)3C

, 25

, 25

CH CH2CH3 + CH3(CH2)3C
CH3

(63%)

CH + CH3CH2

CH2

CH3

. ,
,
,
.
, - -C4H9Li 480

481

- LiN(i-C3H7)2, ,
,
. , 3-1 -
:
Li

H
CH3

C C

CH + 2-C4H9Li

CH3
CH3I
, -25C

(CH3)2C C C

, -78

CH3

C C

Li + 2C4H10

CH3
H2O

(CH3)2C

C CH + LiOH

CH3

CH3

78%

( RCH2Br RCH2I)

sp- .
-1

.
, -
.
6.2.2.

-
.
,
-

,
, ,

481

482

,

200-290
:
C6H5CH CHC6H5 + Br2

2KOH
, 290C

C6H5CH CH C6H5

CCl4

Br

C6H5C

Br

CC6H5 + 2KBr + 2H2O

(88%)

. 150

-1

CH3CH2C

CCH3

:
CH3CH2CH2C CH

KOH
, 175

,
, .
:
CH3(CH2)7CHCH2Br
Br

2NaNH2
NH3; -33C

CH3(CH2)7CH CH(CH2)7COOH
2NaNH3

C9H17C

CH + 2NaBr + 2NH3

Br

Br2
CCl4

CH3(CH2)7CH CH(CH2)7COOH
Br

CH3(CH2)7C C(CH2)7COOH ( )

NH3, -33C

-1
1,2-
-2,5 :
RCH CH2Br

KOH; NR4Cl
-2,5

Br

482

RC CH
(80-85%)

483

6.2.3.

.
,

:
R1C

CH2R2

O
R1

PCl5; C6H5N
C6H5

C C

R1CCl2CH2R2

2NH3
NH3 -

R2 + 2NaCl + 2NH3

(50-75%)

6.3.
-
pKa 25 (. 3). , , ,
pKa :
HC

CH + 2NaNH2

RC CH + C4H9Li

NaC

NH3

RC

CNa + 2NH3

Li + C4H10

(I),
, :
RC

CH + Ag(NH3)2OH

RC

CAg + H2O + 2NH3

.
, - (. 5),
, -.
200 /,
483

484

- 88 /. ,
, -
-,
, .
6.3.1.

, .
, ,
:
HC

Pt

CH + H2

CH2

CH2
Pt

CH2 + H2

CH2 + H; H = - 42 /

CH3

CH3 + H; H = - 33 /

, , ,

:
1

RC

CR + 2H2

Pt Ni

R CH2CH2R

, ,
.
,
( ),
, .

-. -
96%, . . - 5-10%

-.

-
,
14--8Z--1-:

484

485

CH3
CH3CH2CH(CH2)4C

Pd/CaCO3 - Pb(OAc)2

C(CH2)6CH2OH + H2

; 20; CH3CH2OH

CH3
CH3CH2CH(CH2)7

C C

CH3CH2CH(CH2)7
+

CH3

CH3CH2

(CH2)6CH2OH +
H

CrO3 C6H5N HCl

C C
8%

CH

(CH2)6CH2OH

(CH2)7

CH3

CH2Cl2, 20C

(CH2)6CHO
H

- 5% 30
20% +50.

--1--6, :

+ H2

Pd/BaSO4 - Pb(Oc)2
CH3OH;

--1--6-

,---1,6

(i-C4H9)2AlH, -:

485

486

H
RC CH + [(CH3)2CHCH2]2AlH

, -10,

H
CH3OH C2H5OH, -10C

C C

Al[CH2CH(CH3)]2
R

C C
R
R
-

, , -
- :
1) -, , 0
2) CH3OH

98%

,
- 7080 ,
- 0.
-

3-.

3-

:
50-150C

4[(CH3)2CHCH2)3Al + 3H2 + 2Al

6CH2

C(CH3)2 + 2Al + 3H2

50-60
50-70C
50-60

6HAl[CH2CH(CH3)2]2
2[(CH3)CH CH2]3Al

9899%

(
-2-Ni).
1,2- H2NCH2CH2NH2,
:

486

487

CH3CH2

(CH3COO)2Ni; NaBH4

CH3CH2C CCH2CH3 + H2

CH3CH2OH; NH2CH2CH2NH2; 20C

C C

CH2CH3
H

(99%)

HOCH2C C(CH2)4OH + H2

HOCH2

(CH3COO)2Ni; NaBH4
CH3CH2OH; NH2CH2CH2NH2; 20C

C C

(CH2)4OH
H

(98%)

-
33.

(. . 12) ,
.
.

-, - -.
- . -
, . - ,
NH , -
-:

487

488

1) RC CR + Na
..
2) RC

.
CR

..
Na + RC

.
CR

+ NH3

NH2 +

C
H

R
3)

C
H

+ Na

R
Na +

..

C
H

R
4)

C
H

..

+ NH3

NH2 +

H
C

-,

- - (3).
- - -,
, -.
- --
, --,

--. - -
,

(4).

-5 --5 78%
100%.

CH3(CH2)3C C(CH2)3CH3

Na
NH3, - 33

CH3(CH2)3

H
C C

(CH2)3CH3
(78%)

-, -:

488

489

Li
NH3, - 33

CH3(CH2)7C C(CH2)7COOH

CH3(CH2)7

H
C C

(CH2)7COOH

(84%)

CH3
C(CH2)3C CCH3

CH 3

Na
N H 3

H
C C

(CH2)3

H
C

CH3

72%

.
:
O
O; HCl

LiC

HO(CH 2)10Br

(CH2)10Br

HCl, t

CCH2CH3

CH3OH

HO
HO(CH2)10C CCH2CH3

(CH2)10C CCH2CH3

Na, NH3
- 33

(CH2)10

H
C

C
CH2CH3

+
C6H5NHCrO3Cl
CH 2Cl2

-11--1-

O
C
H

(CH2)9

H
C C

CH2CH3

-11-

10--1,

(. 11).
1-
.
HCl ,
-.

489

490

(. 11)
.
- 97
98%
140-150 :
LiAlH4

CH3(CH2)7C C(CH2)7CH3

CH3(CH2)7

, 140 - 150

C C

(CH2)7CH3
(95%)

,
, .

6.3.2.
.
: ,
, .
BH3
3, .
3 1,1 , .


:
R
RC

CH + Sia2BH

(CH3)2CH

CH3 H

, 0

H
C

C
BSia2

BH = Sia2BH
2

Sia2BH -1 0
, :

490

491

RC CH + Sia2BH

H
C C

BSia2

-1
-; BSia2
.
(1,3,2), 65
, :

(CH3)3C

C CH +

(CH3)3C

O
BH
O

, 65

C
B

O
100%

C4H9

C4H9C

CH +

C4H9

O
BH
O

H
C

, 70

H
C
O

C
H

B
O
93%

7%

:
OH
+ B2H6

2
OH

0 - 20 C

O
2
O

BH + 4H2

,
R2BH.

-.

BR2

491

492

(CH3)3C C CCH3 +

BH
O

CH3
C C O
B
H
O

(CH3)3C

65 C

(CH3)C
CH3
O C C
H
B
O

(95%)

(5%)

C5H11C CCH3 +

CH3
C C O
B
H
O

(CH3)3C

BH

65 C

(CH3)C
CH3
O C C
B
H
O

(8%)

CH3
CH3

CH C CH + Sia2BH

65 C

(CH3)2CH

(CH3)2CH

CH3
+
BSia2

Sia2B

(93%)

CH3
H

(7%)

R2BH.
,
,
,
.

-:

492

493

CH3CH2C CCH2CH3

CH3CH2

1) Sia2BH;
2) CH3COOH

CH2CH3
H

(82%)

-
-2-Ni. -

,
:
1)

CH3CH2C

C C

(CH2)10

BH
2

OH

2) CH3COOH; 0
C5H5NCrO3Cl

CH3CH2CH CH CH CH(CH2)10OH
CH3CH2CH CH CH CH(CH2)9

CHO

:
CH3(CH2)5

H
C C

I2 - CH3ONa

CH3OH

CH3(CH2)5

H
C C

I
(80%)

. , BR2-
, 5.
,
, .
(. . 16)
. ,
,

493

494

,
:
CH3(CH2)3C

CH

, 0

CH3(CH2)3

CH3(CH2)3

Sia2BH

1) NaOH

C
BSia2

2) pH 7 - 8; H2O2

H
C C

CH3(CH2)3CH2CHO

OH

(88%)

CH3CH2

1) Sia2BH

CH3CH2C CCH2CH3

2) H2O2; NaOH; H2O

C C

CH2CH3
OH

O
CH3(CH2)2

C CH2CH3

(97%)

.

, -
.
,

(. . 6). 9(3.3.1)

(9-)

, .

:
CH3CH2CH2C

CCH2CH CH2

CH3CH2CH2C

1) 9- -
2) H2O2; NaOH; H2O

CCH2CH2CH2OH

494

495

:
R

H
C C

1) Hg(OAc)2, CH3OH

C C

2) NaCl

HgCl

. -,

-1,3-:
(CH3)3C

H
C

(CH3)3C
1) CH3ONa

2) CuBr S(CH3)2

H
C

H
C C
C(CH3)3

E, E-1,3-
(98%)

, 1015 .

6.3.3.

1,2- .
,
1,2- .
RuO4 (VIII)
1,2- .

, ,
78 0 . , , 7,5 .
:

495

496

CH3(CH2)7C

CH3C

KMnO4
H2O; pH 7,5; 5

C(CH2)7COOH

CCH2CH3

KMnO4
H2O; pH 7,5; 0

CH3(CH2)7C

C(CH2)7COOH

O O

CH3C C CH2CH3
O O
(90%)

R1C

KMnO4
H2O, t

CR2

R1COOH + R2COOH

,
.
,
.

. , 6
:
CH3(CH2)10C

KMnO4
H2O, t

C(CH2)4COOH

CH3(CH2)10COOH + HOOC(CH2)4COOH

-1,
( ). 1870 .
, (I),
1,3-:
C6H5C

CH + Cu2Cl2

NH3

C6H5C CCu

O2

C6H5C C C CC6H5
(90%)

HOOC

C C

Cu

K3Fe(CN)6

HOOCC

C C C

COOH

(60%)

C4H9C

CH + Cu2Cl2 + O2

C5H5N; 60

C4H9C C C C C4H9
(90%)

496

497

(I)
(III) K3[Fe(CN)6] .
1959 .
. (II)
6070 .
,-.

-1,5 (. , 1960):
Cu(OAc)2

C5H5N

6%

6 - 10%

,
-1,5.
[18]- (
. . 12). -1,8

1,3,10,12-

Cu(OAc)2
C5H5N

10%

-1 ( )
(I) ( , 1957 .):
C6H5C

CBr + HC C(CH2)8COOH

Cu2Cl2
C2H5N; CH3OH

497

C6H5C

C C

C(CH2)8COOH

(98%)

498

C6H13C

Cu2Cl2

CBr + HC CCH2CH3

CH3(CH2)9C

CBr + HC C(CH2)6CH2OH

CH3(CH2)9C

C C

C6H13C

C4H9NH2; CH3OH

CCH2CH3

(90%)

Cu2Cl2
CH3OH; C4H9NH2; NH2OH HCl; 0 - 5

(CH2)6CH2OH

(84%)

-1
:
C6H13C CH

C4H9Li
, - 78

C6H13C CLi

Br2
, - 78

C6H13C CBr + LiBr

Cu2Cl2 -1.
6.3.4.

.


.

. ,
(. 2),

. ,

,
. +
+ (.

498

499

5). + +
-. sp- ,
- -. sp-

sp - , - :
Csp - Csp2

H
+

1,075 A

1,263 A

1,086 A

H
-

,
, -
,
. . 6.3

, 25 .

f /
261

CH3

219

CH3CH2

208

CH3CH2CH2

187

CH3CHCH3

174

(CH3)3C

499

500

CH2

226

CH CH2

CH2
CH2

266

CH

237

C CH3

218

CH3CH C CH3

, . 6.3, , - 47
/ , -.

CH3CH2Cl CH2=CHCl:
CH3CH2Cl

CH2

CH3CH2 + Cl + f = +191 /
CH2

CHCl

CH + Cl + f = +223 /

, -
- -

. . 6.4
, - ,
, -
.
6.4

2=CH2/

1,14104

49=2/49

1,8105

65=2/65

2,6103

65=2/65

7,2102

49=2/65

5,3105

25=25/2525
4-

2=2/

-Cl6H4SeCl

49=2/49

500

1105
2,8104
840

501

65SeCl

65=2/65

1,8102

2=2/

5,6104

49=2/49

6,9103

65=2/65

1102

49=2/49

5,2

65=2/65

0,8

25=2/25

2,6

49=2/49

3,6

25=25/2525

16,6

65=2/65

0,65

,
.
,
102

105 , . ,

, ,
, :
CH2

CH CH2CH2

CCl

4
CH + Br2 - 20

CH2

CH2

Br

Br

CH2CH2

C CH

(97%)

,
(II),
. ,
, .
, ,

501

502

C2H5C

NR4 Cl
CH3COOH; 10

CC2H5 + HCl

C2H5

Cl

C2H5
(97%)

C2H5

H
C

+ HCl

Cl

NR4 Cl
CH3COOH

C2H5

C2H5CCl2CH2C2H5
(78%)

6.3.4..

: AdE2 - AdE3.
AdE2
-, -
-. -
- -

- - -
.
Cl
ArC

Ar

H
C C

Cl

AdE 2
CH3COOH

R + HCl

H
C

Ar
Ar

H
C

Ar

H
C C

Cl
+

Ar

Cl

R
H

C C

+
CH3COO

502

Cl
CH3COOH

+
R

CH3COO
Ar

H
C C
R

503

- -
AdE2-
,
.
AdE3-

- -
. AdE3-
.
H X

H X
C

R1C CR2 + 2HX

R1

R2

H X

R1

R1

H X

R1
C

R2
H
C C

R2

+ HX
R2

AdE3-
- .
AdE3-
. AdE3 AdE2.

AdE2-

.
HCl 25 (92%) (8%) 12:1.


:
C6H5C

CH + DCl

C6H5
CH3COOH

Cl

H
C C
D

AdE2-

1-. HCl 1503

504

70% -
19% -:
1

C6H5

C C

C6H5

CH3 + HCl

CH3COOH

CH3

Cl

C6H5
+

H
C C

Cl

(70%)

CH3
(19%)

AdE2-
-2 .
, -2
300 -1,
.

AdE2-.

AdE3-
2-5 .

AdE3-. 3 -
(40%) - (7%)
-3:
CH3CH2C

CCH2CH3 + HCl

CH3CH2
CH3COOH

Cl
C C

C6H5

CH2CH3

Cl

(40%)

CH2CH3
H

(7%)

+ C3H7

C C2H5
O
(53%)

(CH3)4N+Cl

-, 3-4% -
:
+

CH3CH2C

CCH2CH3 + HCl

N (CH3)4 Cl
CH3COOH

CH3CH2

Cl
C

C
CH2CH3

(96 - 97%)

+ C3H7COC2H5
(3 - 4%)

. , AdE2 AdE3
,
. ,

504

505

,
- .
6.3.4..
(
FSO3H, CF3SO3H)

.
, (FSO3
, CF3SO3, ClO4). AdE3-
, FSO3 CF3SO3,
AdE2-. ,
- -1, -1
-1 - SO2FCl 120
Z- - 80:20:
H

R
RC

CH + FSO3D

SO2FCl, -120

C C
FO2SO

+
D

Z- (80%)

FO2SO

H
C

D
E- (20%)

R = CH3, C2H5, C4H9, C6H13

-.

-

. Z- -
, -, ,
-
- -. -
Z- -
.

505

506

:
CH3CH2C

CCH2CH3 + FSO3H

CH3CH2

FO2SO

SO2ClF, -120 C

CH2CH3

CH3CH2
+

H
C C

FO2SO

(51%)

CH2CH3
(49%)

-3 60
89%- E- Z--3.

.
;

:
RC

CR + CH3COOH

(CH3COO)2Hg
CH3COOH

RCH2

(CH3COO)2Hg
CH3COOH

C(

RCH C

OCOCH3
R

OCOCH3)2

,
- .
6.3.4..

506

507

, :

v = k2[][Br2] + k3[][Br2]2 + k[][Br2][Br],

.. - .

:

= k2[][Br2]

- , .

:
R
RC + Br2

CH3COOH

Br
C C

Br

R
(99%)

R
RC

CR + Br2

R
C

HCl2CHFCl; -78 C

Br Br 3-

Br
C C

Br

Br

-
-, -. - Z

Z-

1--2--1-

- .

-
. -
:
X C6H4C CH + Br2

LiBr
CH3COOH

Br

H
C

X C6H4

Br
(>99%)

507

508

. -3 -2
- -
:
+

C2H5C

CC2H5 + Cl2

NR4 Cl

Cl

C2H5

CH3COOH

Cl

C2H5

-:
CH3C CCH3 + Cl2

CH3COOH

CH3

CH3

Cl
C

Cl

+
Cl

CH3
20%

CH3

Cl

CH3

OAc
5%

CH3

OAc
C C

+
CH3

65%

Cl

CH3
Cl

3%

.
- Z- 55:45, - Z .
-,
- .
,
.
-, .
,
,
. , ,
AdE2 -, -
() .
( )

-, -.
508

509

, - .
-,
,
. -
- - ,
.
- .

.
Cl

R1
C C
Cl

Cl

R2

C C
Cl
R1
- ()

R2

Cl
R1C C

Cl -
Cl

R2

R1 = t-Bu
R1 = Ar
R2 = H, CH3, t-Bu R2 = H

R1 = Ar
R2 = Alk

R1C CR2 + Cl2

R1 = R2 = Alk

Cl

C C
R1

R2
-

R2
R1
-

-
()

R1 Cl
R2
C
C

R1

Cl

Cl
C C
R2

509

-
+ (
)

R1 = R2 = Ar

Cl

Cl

C C
Cl

R2
R1 Cl
C
C
Cl

Cl
R1 = Alk
R2 = H

Cl

510

Hal
Hal

Hal
R1

C C

2
R
-

Hal
Hal
C C

R1

R1 = Ar
R2 = Alk

R2

R1C

R1 = Ar
R2 = H

CR2 + Hal2

R1 = R2 = Ar

Hal

R1 = Alk
R2 = H

Hal
C C

R1

R2

R1 = R2 = Alk

Hal
C
R1

Hal

Hal
C
R2

C
R1

Hal
C
R2

- AdE2 AdE3

- -
.

-,

- -,
-.


-.

AdE2 AdE3 - ,

510

511

.
.
6.3.4..
1881 . . . ,

. ,
.
, .
(. . 17).
:
R

RC

H ; Hg2+
H2O

CH + HOH

H
C

HO

R C CH3

RC CR + HOH

H ; Hg2+
H2O

H
C C

HO

O
R C CH2R

(II)
. ,
, ,
:
OH

H2O; H ; Hg2+

C CH

OH
C CH3
O
(65-67%)

CH3CH2CH2C CCH2CH2CH3 + H2O

H ; Hg2+
H2O - CH3COOH

CH3CH2CH2CCH2CH2CH2CH3
O
(89%)

511

512

C6H5C

H ; Hg2+

CCOOH + H2O

C6H5

C CH2COOH
O
(75%)

(III),
(I), (III).
. ,
- .
, ,
- .
.

D2 D2S4 2,5
2-H2S4. ,
, .
, -,
.
6.3.4..

-
:
:
R1
R1C

SR2
C

CH + R2SCl
Cl

+
H

Cl

R1
C
R2S

C
H

-1
. , , 2,4-

512

513

:
C6H5C

C6H5

CH + ArSCl

CH2Cl2; 25 C

SAr
C C

Cl

H
(100%)

,
-
SAr Cl:
CH3
CH3 C CCH3 + (CH3S)2 SCH3

CH3
C

SO 2
-80 C

C
S SbCl6

SbCl6

+ CH3

CH3

CH3

SO2 -80

C(CH3)3

(CH3)3C
(CH3)3CC

CC(CH3)3 + (CH3S)2SCH3
SbCl6

SO2
- 80 C

C
S

SbCl6

CH3
+20

ArSCl 2 -1. ,
- ,
-.

-, )
, )
,
(, , 1968).
,
, 80 ,
, :
513

514

C(CH3)3

(CH3)3C
(CH3)3CC

CC(CH3)3 + CH3SCl

CH2Cl2,
0 C
CH3SCl

Cl
C

(CH3)3C

SO2
- 80 C
+

C
S

Cl

CH3

NR4 Cl
- 10 C,
SO2

C(CH3)3

AgBF4

C(CH3)3

(CH3)3C
C

SCH3

C
S

BF4

CH3
+20

BF4.
- -.
,
, ,
. RS+ 1 1- -,
- .
CH3S+ 40
:
C6H5

CH
C

CH3

- 40 C
- 70 C

CH
C
CH3
CH3S

C6H5

CH3

(Cl,

Br

.)

,
:

514

515

CH3

S
CH3
Cl
CH3

Cl

CH3S

Cl

C6H5

H + Cl

Cl

SCH3
H

, -
- .

.


:
C6H4-Cl-
S
RC

CHCl2CHCl2

CH + -Cl-C 4H 6SCl

R
Cl
R

S
C

Cl

C6H4-Cl-

-Cl-C 6H 4

Cl
S

H
C C

Cl

R = C2H5
(27%)
R = (CH3)2CH (10%)
R = (CH3)3C (0%)

(73%)
(90%)
(100%)

. : < <

515

516

-,
.

,

RSCl

RSCl

:
R

R
C

RC CR + ArSCl

R
C

S Cl

S
Ar
Cl

Cl

Ar

R
C

SAr

, ,
-
,

-.

516

517

C6H5
Se Cl

RC CH + C6H5SeCl

R
Cl

H
C

C6H5Se

+
SeC6H5

H
C C

Cl

6.3.4.. .
AlCl3
-,
.
- -:
R1

AlCl3

R1C CR2 + R C

R C

CH2Cl2; - 40 C

R2

X + R C

R1
C

C
R2

-, -:
O
CH3C CCH3 + -CH 3O C6H4COCl

CH3

AlCl3
CH2Cl2; - 40 C

C
C C

Cl

C6H4COCl-

CH3
(100%)

CH3C

CCH3 + -O2N

CH3
Cl

AlCl3

C6H4COCl

COC6H4

CH2Cl2; - 40 C

NO2-

CH3

CH3
+

C C

Cl

C
O

(37%)

517

CH3
C6H4
(63%)

NO2

518

CH3C

CH3

AlCl3

CCH3 + Cl2CHCOCl

CH2Cl2; - 40 C

C C

Cl

(100%)

CH3
COCHCl2

6.3.5.

,
. , --

X-Y
,
(. 5).
X Y

X +Y
H
C

: ) X + RC CH
H
C

H
C

Y
+X Y

+X
X

-, --

17-23 /,

X-Y .
HBr

518

519

CH3C CH + HBr

h
- 78 C

H
C

CH3

Br

+ CH3CBrCH2Br

(70%)
-

CH3C

CBr + HBr

CH3

h
- 78 C

Br

(30%)

H
C

(75%)

Br

O
HC

h
- 78 C

C COH + C6H5CH2SH

C6H5C

H
C
C6H5CH2S

(74%)

(68%)

SCH2CH3
H

Br
C C

Cl3C
H

(PhCOO)2

CF3I

(CH3COO)2

CH + BrCCl3

CH3C

COOH

C6H5

CH + CH3CH2SH

CH3(CH2)5C

(80%)

(CH2)5CH3

I
C

CF3

CH3
(86%)

-1
,
, ,


:
H
R1C

H
C C

CH + R2SH
R1

SR2

H2O; H ; Hg2+

R1CH2CHO

- - :
519

520

CH3(CH2)5C

Br

H
C
Cl3C

C
(CH2)5CH3

Br

NaOH
H2O

(CH3COO)2

CH + BrCCl3

CH3(CH2)5

COOH

, .. ,
,
1:1 2:1.
HBr -


.


N-. 1--5 N- 95% 5%
:
CH2

NBS
CCL4; 80 C

CHCH2CH2C CH

CH2

CH CHCH C
Br

CH + BrCH2

(95%)

CH CH CH2

C CH

(5%)

6.3.6.
sp-
sp2- .
,
,

520

521

.
. , -,
-
-,
:
HC

200
ROH

CH + RO

ROCH CH

ROH

ROCH CH2 + RO

.
- ;
Cu2Cl2 (I) .
,
:
HC

CH + HCN

Cu2Cl2
HCl

CH2

CHCN

(. . 28).
-
. , :
H
CH3C CCH3 + RSH

CH3CH2OH, NaOH

CH3
SR

CH3
H

CH3(CH2)5C

CH + RSH

CH3CH2OH, NaOH

H
C

CH3(CH2)5

C
SR

6.3.7. -


. .

521

522

1888 . -1 2,2-
170 .
-1 -2.
(I) -
-1.
85%- .
(. . 3.9) -2 ().
2,2- 120
-1, 170180 -2:
CH3
Cl

CH
KOH
; 120 C

Cl

CH2

C
CH2

CH3

CH3
KOH
; 170 C

C
C

CH3

CH3

, -1 -2
.

-2

170

3--1,2,

:
CH3

CH C

CH

KOH
; 170 C

CH3

C C

CH2

CH3

CH3

(98%)

(C6H5)2CH C C

C6H5

Al2O3 .

(C6H5)2C

CHC6H5

(83%)

522

523

.
,

,
, -1
-3 .
:
-

C2H5O , t

R CH C CH

RCH C CH

C2H5OH

H
-

C2H5O , t

RC

C2H5OH

CH2

C2H5OH
-

C2H5O , t

C2H5OH
-

C2H5O , t

RC

RC

C CH2

CCH3

.
(. 5) .
, :
CH3CH2CH2C CH
(1,5%)

KOH
, 175 C, 3

KOH
, 175 C, 3

CH3CH2

CH C

CH2

(3,5%)

CH3CH2C C CH3
(95%)

1,3- () 1,3-
1,2- 1,2- 20 2-30
:

523

524

K NH(CH2)3NH2 (KAPA)

CH3(CH2)5C C(CH2)5CH3

CH3(CH2)11C

NH2(CH2)3NH2; 20 C; 5

CK

H2O

CH3(CH2)11C CH
(89%)

Li NH(CH2)3NH2 (KAPA)

CH3(CH2)3C C(CH2)5CH3

CH3(CH2)9C

NH2(CH2)3NH2; 20 C; 30

CLi

H2O

CH3(CH2)11C CH
(85%)

HOCH2

Li NH(CH2)3NH2 (KAPA)

C C(CH2)5CH3

NH2(CH2)3NH2

H2O

LiOCH2(CH2)6C CLi

HOCH2(CH2)6C CH
(87%)

.
, 1,3-
1,2-.

.

6.3.8.
1900 . . . ,

.

, :

524

525

R1 +
KOH
C O + HC CH .
R2

R1
C OK

C CH

R1

HOH

R2 C CH

OH

R2

.

:

HC

CH + NaNH2

N H 3

HC

- 33 C

O Na

CNa

N H 3 - ; - 33 C

OH

NH4Cl
H2O; 0 C

C CH

C CH
(85%)

O
CH3S

CH3

O
NaH
; 70 C

CH3S

CH2Na

HC CH
-

O
CH3C

HC

CNa

H
-

OH
C

CH3

C CH

, 17-- -
,

525

526

CH3

CH3

OH

HC

CH; KNH2
N H 3 -

CH

(90%)

HO

HO

17--

1925 .
.
, 100 .,

- -2--1,4:
HCHO + HCHO + HC CH

Cu

C C
100

Cu

HC CCH2OH + HOCH2C CCH2OH

-2--1,4

-1,3

:
HOCH2C

CH2

H2; Ni

CCH2OH

HOCH2CH2CH2CH2OH

H3PO4/SiO2
400 - 500 C

CH CH CH2 + 2H2O

-1,3

(. 28).
6.3.9.


.
, ,
, 700 .
,

526

527

(. , 1860).

, 20-100 .

- , -
-1,3,5,7.

Ni[(C6H5)3P]2(CO)2, , : ()2; CpRh(CO)2;

PdCl2(C6H5CN)2,

=55

(. , 1948):
3HC

CH

(CO)2Ni[P(C6H5)3]2
60 - 70 C; 15
(80%)

,
1,2,4- 1,3,5- :
R
RC

CH

(CO)2Ni[P(C6H5)3]2

70 C;

CH2OH
HC CCH2OH

CH2OH

CH2OH

(CO)2Ni[P(C6H5)3]2

70 C;

CH2OH

HOCH2

CH2OH

1 : 1
(95%)

1,3,5- 1,2,4 -1
- (-49)3Al-TiCl4. 1,3,5---,
1,3,5- 1,2,4-:

527

528

(CH3)3C
3(CH3)3CC

CH

C(CH3)3

(-C4H 9)3Al, TiCl4

20 C

C(CH3)3
(90%)

CH2
3CH2

CH C

CH

CH

CH CH2

CH CH2

(-C4H9)3Al, TiCl4

CH CH2
+

20 C

CH CH2

CH CH2
1 : 9

.
, -()

:
CH3OOC
Pd

LnPd0 + 2CH3OOCC CCOOCH3

CH3OOC
H3COOC
CH3COOCC

CCOOCH3

COOCH3

H3COOC

COOCH3
COOCH3
COOCH3

H3COOC

COOCH3

.
:

528

529

R
2RC

LnM

CR

R1C

LmM

R1

CR1

LmM

LmM

R1

R1

R1

R1

+ LnM
R1

R
R

.
,
. , 1,3-, ,
, - (. 7)
.

,- :
C CH
(CH2)n

+ RC CR

(CO)2Co(C5H5)

C CH

140 C

R
(CH2)n
R
R = Si(CH3)3,
n = 1, 2, 3

()2(65).

,-,

-().

529

530

-1,3,5,7
.
. 1943 .,
.
Ni(AcAc)2
.
-1,3,5,7
80 - 120 10-25 .
Ni(AcAc)2
; 80-120 ; 10 - 25

4CH CH

(70%)

20-40%
,
.

80-90% .
, -
.
.
6.3.10.
,

.
RCCR,

ArCCR.

ArCCar

. ,
,

5 15%:
530

531

(CH3)3C
(CH 3)3C

(C2H5)3NCH2C6H5Cl

C(CH3)3 + CHCl3

C C

C(CH3)3
C
C

50%- N aOH ; H 2O

Cl
(CH3)3C

H2O
OH

Cl

C(CH3)3
C

C
(6,5%)

C
O

C3H7
C3H7C

CC3H7 + CCl3COONa

C3H7
C

80 C

C
C

Cl
C3H7

H2O

+ CO 2 + NaCl

OH

Cl

C3H7
C

C
C

(5%)

+ CHCl3

C C

(C8H17)3NCH3Cl
CHCl3

(15%)

C
O

C6H5HgCCl3
,
:
(CH3)3C
(CH3)3C

C C

CH3 + C6H5HgCCl3

C(CH3)3
C

Cl

(. 12):

531

(14%)

Cl
,

532

C6H5

C6H5
C

C6H5C

CC6H5 + CHBr3 + (CH3)3CO K

C
Br

C6H5

C6H5
C

C6H5

C
Br

Br

C6H5
C

HBr

H2O

OH

.
, ,
,
:
Cl

Cl
C

CH3

C C C

CH3C

CH2 + :CCl2

C C
CH3

CH3
Cl
CH2

C C
CH3

CH2

Cl

Cl

C CH2 + :CCl2

CH3

Cl

CH3

CH3
(62%)

(II) :
C3H7
C3H7C

CC3H7 + N2CHCOOC2H5

CuSO4
70 C

C3H7
C

C
C

(90%)

H COOC2H5

532

533

.
, :

RC
RC

CH + N2CHCOOC2H5

Rh2 (OAc)4
25 C

CH
C

(68-84%)

H COOC2H5

,
.

533

534

7.

7.1. 1,3-
7.2. 1,3-
7.3.
7.4.
7.4.1.
7.4.2. [4+2]- (
)
7.4.2.. -
7.4.2..
7.4.3.
7.4.4. 1,3-

7.5. ()
7.5.1.
7.5.2.
7.5.2..
7.5.2..
7.5.2..

7.5.2..
7.5.3.
,

,
.. ,
. ,

,
..
: ,
. , 1,2-,
. 1,2,

-1,2,

:
534

535

CH2

C CH2

1,3-, -1,3,
-1,3 .. 1,3,5-
, 1,3,5,7- ,
1,3,5,7,9-.
,
. , , 1,4-, 1,5- .
.
,
.
,
.
1,3, .

7.1. 1,3-
- -1,3:
H
H
1,47

1,34

H
119,5 C

122,9 C

1,34

, 12 34 (1,33 ), 23
-
(1,54 ). 2-3 -1,3
--
.
. sp2 - 2-3

535

536

sp2- . - -
sp3-
, - Csp2-Csp2. . 7.1 - .
, . 7.1, , -
sp3- s-

,
.
-1,3 .
57 /.
7.1
-

H3CCH3

sp3 - sp3

1,54

CH2=CHCH3

sp2 - sp3

1,50

CH2=CHCH=CH2

sp2 - sp2

1,47

HCCCH3

sp - sp3

1,46

HCCCH=CH2

sp - sp2

1,43

HCCCCH

sp - sp

1,37

CH2

CH CH CH2 + 2H2

-C4H10 + H /

H = - 57,1 /

30,3 / (. . 5).
-1,3

60,6

. 3,5
/
-1,3. . . -
Csp2-Csp2 , - Csp3-Csp2
. ,
.

536

537

-1,3
.
-1,3 -
(. . 2) 1,3-
.

7.2.

1,3-

1,3-

- .
,
.
- *-,
171 -*- .
217 1,3- 1,3-
2 *3 (. . 2 . 7.1).

2 *3 1,3-
(. 7.1).

4
2()

3()

2()
1()
CH2

CH2
CH2

CH

CH

CH2

. 7.1. -
1,3-

537

538

1,3-.
,
,
-

(.

7.2).

268
-1,3,5- 310 -2,4,6,8- 447

-, 11 . ,
, ,

, .. (. 2).
, - ,
1,3-, ,
.
.
,
180 . , 1,4-
178 , .. , .

max

max

CH2=CH2

171

15 350

184

10 000

182

7 600

-2-

CH3CH2

CH2CH3

1-

CH3(CH2)5CCH

185

2 000

1,3-

CH2=CHCH=CH2

217

21 000

223

23 000

-1,3-

CH3

H
C

C
CH CH2

1--3-

CH2=CHCCH

228

7 800

1,4-

CH2=CHCH2CH=CH2

178

538

539
1,3-

H
--1,3,5

--1,3,5,7

310

42 700

H
C

36 000

C C
H

268

C C

3 400

C C
H

239

C C
H

C C
H

H
C C

1,3- ,
S- S-.
H

H
H

= 3,9 /

H
H

S-

S-

,
1% S-- 99% S-. ,
(2)-(3) (S single),
- - .

S--

(1) (4).

7.3.

. -1,3, (2-1,3)
(, .), .
-1,3
- ,

539

540

. (III),
Al2O3.

,
(I)
.
Cu2Cl2; NH4Cl

HC CH + HC CH

CH2

CH2

H2O; 5 C

CH

Cu2Cl2

CH C CH + HCl

CH C

CH2

H2O; 5 C

CH C

CH2

Cl

:
CH2

CH CH CH2 + Cl2

CH2ClCH CHCH2Cl

CH2

CH CHCl

300 C

Cu2Cl2; 100 C

CH2Cl + NaOH

CH2ClCH CH CH2Cl + CH2ClCHClCH CH2

CH2

CH CHCl

H2O; 100 C

CH2

CH2Cl

CH C

CH2 + NaCl + H2O

Cl

() .
, .


-
1,4- (. . 6).
1,3-
,

540

541

15-20 .
1,3- 1,3-,

-1 - (. . 6).
1,3- Pd/CaCO3
, 4050% Z,Z-1,3-, 20% 30-40% .
1,3- P-2-Ni Z,Z1,3- :
H
R1C C C

CR1 + 2H2

R1

P-2-Ni
C2H5OH; 20

R2
H
Z,Z-1,3-

Z,Z-1,3-

. , ,
.
H
C4H9C

C C

(CH2)3

CH2OH

1) (C6H11)2BH;

-C4H9

2) CH3COOH

(CH2)3CH2OH
H

,-1,3- .

(-), . -

(. . 6.3.1).
(I) ,-1,3-:

541

542

R1C

CR2 + [(CH3)2CH

CH2

AlH

R1

- 20 - 0

R2
C

Al

CH2

CH(CH3)2]

R2
Cu2Cl2

R1

R1

; - 20

R2
E,E-1,3-

, , .
,-1,3
() (I):
(CH3)3C

(CH3)3C

H
C

1) CH3ONa; 0

BSia2

2) Cu2Br2 . S(CH3)2; 0

H
C C

H
C

C
C(CH3)3

Sia = (CH3)2CH CH
CH3

.

.
, ,
-

(. 27).
. -
, -
.
-
020 1,3- ( 7090%).
- ,

542

543

R1
C

Li
+

Br

R2

R4
C

Pd[P(C6H5)3]4

R3

R4

R1

H
R2

R3

, . -
- .
-

Pd[P(C6H5)3]4 -
(. 27) ,-
,Z-1,3-, :

R1C

CH

C C
H

R1
C

R1

-
, 0

Al(i-C4H9)2
Br

R2
+

Al(i-C4H9)2

C C
H

Pd[P(C6H5)3]4

H
C

+
Al(i-C4H9)2

R2
C
H

C
Br

R2
C

C
H

Z-

R1

R1

E,Z-1,3-

R1
C

Pd[P(C6H5)3]4

R2

E,E-1,3-

,
,- ,Z-1,3- .

1,3-
( . . 19).
Cu2Br2 Cu2I2:

543

544

Br
C

C4H9Li
, - 78

Li
C

Cu2Cl2

, - 20

Cu
C

Li
H

R
O2

, - 20

0 . ,- 1,3- ,

:
R

H
C

C
HgBr

R
; 0 - 10

H
C

Li2PdCl4 (LiCl + PdCl2)

H
C

E,E-1,3-

7.4.

7.4.1.

,
, ,
1,2- 1,4-, ..
:
CH2

CH CH CH2 + HBr

CH3CH CH CH2

CH2BrCH CH CH3

Br
3--1-
( 1,2-)

CH2

CH CH CH2 + Br2

1--2-
( 1,4-)

CH2

CH CH CH2 + CH2Br

Br

Br

3,4--1-
( 1,2-)

CH CH CH2Br

1,4--2-
( 1,4-)

1,2-, ,

544

545

1,4-
. + -

,
(1) (3), -
:
+

C C C C

+H

C C

,
1,3-, - (1) (3)
1,4 1,2-:
CH2

CH CH CH2 + H

CH3

CH3CH

CH CH CH2

CH

CH3

CH2

CH CH CH2Br

1,4-

Br
1,2-

:
CH2

CH CH CH2 + Br2

BrCH2

BrCH2CH

CH CH CH2

CH

BrCH2

CH2 Br

CH CH CH2Br

1,4-

Br
1,2-

1,2- 1,4-
. ,
, 1,2- 1,4- HBr 1,3-

545

546

80 +40
:
CH2

CH CH CH2 + HBr

CH3

CH CH CH2 + CH3CH CH CH2Br

Br

80 :

80%

20%

0 :

70%

30%

+40 :

20%

80%

1,4- .
1,3:
CH2

CH CH CH2 + Br2

CH2

CH CH CH2 + CHCH CH CH2Br

Br

Br

Br

80 :

80%

20%

15 :

54%

46%

+40 :

20%

80%

+60 :

10%

90%

1,2-

1,4-

, + Br+ 1,3-,
Br (1) (3)

1,2-

, -
-.
, 1,2- 1,4-
1,3- 80 +40,
1,2-
1,4- HBr +40:

546

547

Br
CH3CH CH CH2 + CH3CH CH CH2Br
- 80

CH2

(80%)

(20%)

CH CH CH2 + HBr
+40

CH3CH CH CH2 + CH3CH CH CH2Br

Br

(20%)

(80%)

1:1,
1,3- 15 ,
+60 90% - - 1,4:
BrCH2CH CH CH2Br

BrCH2CH CH CH2Br

(46%)

(90%)
+60

+
BrCH2

-15

CH CH CH2

BrCH2

Br

CH CH CH2
Br

(54%)

(10%)

1,2- 1,4,

.
,
(, ) . ,
, ,
.
,
, ,
, ,
, G<G.
, GC>G.
, ,

1,2-

1,4-.

.
. 7.2.

547

548

GC

. 7.2.

, , GC>G,
, .
, , , .

.
.
,
G<G,
. , ,
.
,
.
.
80 HBr Br2 1,3
1,2- 1,4- 4:1. +40
.
-

548

549

-. - (1), (3).
1,2- 1,4- ,
1,4- ( ). 1,4-
1,2-,
1,4-
, 1,2- - .
(. 5).


.
. 7.3
1,3-.

CH3CH CH CH2
Br

CH2

CH CH CH2
+
+H

CH3

CH CH CH2

-Br
+Br

1,2-

+Br
-Br

CH3CH CH CH2Br

1,4-

.
,
,
, ,

, 1,3-.

549

550

,
,
.

.
1,4 .
1,2-:
CH2

CH CH CH2 + C6H5SCl

CHCl3; 20

C6H5S

CH2CH CH CH2
(98%)

1,3-
,
:
CO3H

COOH

CH3

CH3
+

CH3

Cl

CHCl3; 60
(77-83%)

CO3H

CH3

CH3

CH3

Cl

CH3

COOH

CH3
C6H6; 5

HO

+
HO

O
(78%)

1,3-
[1+2]-.
, .
; , ,
:

550

551

Cl
Cl
2CH2

CH CH CH2 + CHCl3 + NaOH

(C2H5)3NCH2C6H5Cl
H2O

+
Cl
Cl
(42%)
(6%)

Cl
Cl
Cl
Cl

2CH2

NaOH;(C2H5)3NCH2C6H5Cl

CH CH CH2 + 2CHCl3

H2O - CHCl3

+
Cl
(13%) Cl

Cl
(38%) Cl

:
Cl

Cl

NaOH;(C2H5)3NCH2C6H5Cl

+ 2CHCl3 + NaOH

(97%) -

H2O

Cl

Cl

1,2-
. -1,3 3
1,2-.
1,6-:
CH2

CH CH CH2

BH3

CH2
H
B
H

CH

CH2

CH

CH CH2

BH3

CH2

CH2

CH CH2

CH2

B
H

CH2

B
H

, BR2
.
,

551

552

.
,
1,4-:
CH2

CH CH CH2 + 2Sia2BH

HO CH2

CH2

CH2

CH2

BSia2

CH2

H2O2; NaOH

CH CH CH2

H2O

BSia2

OH

(90%)

7.4.2. (4+2)- (
-)
1928 . . .

,
-. 1,4
, :
O

CH2
CH
CH
CH2

O
O

, 100 ; 5

O
(90-100%)

, -
[4+2]-,
4- 2-
. . [4+2], , .
- -
- 1 - .
- , -, [4+2]-,

, , . ,
.

552

553

.
,
. ,
- , , ,
. -
, 1,3-,
S--. ,
S--, , ,
, :

(CH3)3C

CH CH

CH CH C(CH3)3

- ,
, ,
,

[4+2]-

.
7.4.2.. -
- .
,
- . ,
.
1,3-
:
H
C

COOCH3

H
COOCH3

150

C
H

COOCH3

(68%)

553

COOCH3
H

554

H
C

COOCH3

H
COOCH3

200

C
COOCH3

(95%)

H
COOCH3

- , -
.
- .

- ,
.
.
,
, :
O

O
+

H
CH3COOC2H5
25

+
O

H
H

O
O

O
- (99%)

- (1%)

,
:

25

,
- . -

,
.
-
. -

554

555

.
-:

CH2

CH COOCH3 +

COOCH3

COOCH3

- (76%)

- (24%)

-- , -,
.
7.4.2..
-
.
- ,

, .
. 7.3
- .
- , ,
,
.
O
O
1. CH2

C C CH2 + CH2

CH C
H

H3C

100
5

H3C
(90%)

555

556

CH3
2.

H
H

H3C H

O
+

O
O

; 25

CH3

H3C H

(100%)

COOCH3

COOCH3
3.

+
COOCH3

COOCH3
(68%)

O
4.

O + CH3OOC

C C COOCH3

COOCH3

90
8
(77%)

COOCH3

NC
NC

CN
CN

+ (NC)2C C(CN)2

5.

(79%)

6.

OCH2CH3

COOC2H5

160
15

(94%)

CH3
7.

H
H
CH3

H CH3

COOCH3
+

COOCH3

100

COOCH3

COOCH3

H CH3
(100%)

556

557

O
8.

; 100
48

; 30
3 .

(80-90%)

+ C6H5N O

O
(70%)

H3C
9.

H3C

C6H5

(66%)

CH3
H

10.

H CH3
N

+ H5C2OOC N N COOC2H5

COOC2H5
COOC2H5

H CH3

CH3

(94%)

Cl

Cl

Cl

Cl
Cl

Cl +

11.
Cl

Cl

Cl

Cl

Cl

()

[4+2]- . . 1950 .

-. ,

. 25,
.

7.4.3.
1,3-
,
.
,
557

558

.

(. 28) ,
,
, , .
, . ,
1,2-, 1,4-, 1,4 .

: , , , (Fe2+ H2O2).
:
Fe2+ + ROOH
RO + CH2

Fe3+ + HO + RO

CH CH CH2

RO CH2

CH CH CH2

:
RO CH2
CH2

n CH2

CH

CH

CH CH CH2 + CH2
CH

CH

CH2

CH2

ROCH2
ROCH2

ROCH2

CH CH CH2

CH CH CH2
CH CH CH2

CH2
CH2

CH CH CH2

CH CH CH2
CH CH CH2

CH2
CH2

CH2

CH CH CH2

CH CH CH2
CH CH CH2

CH CH CH CH2

...

CH CH2

CH CH CH CH2

...

CH2

CH CH CH2

...

1,4-, 1,2-,
,
.
.
,
.
+5+50
.

558

559

(76%)

(24%)

- ):
n CH2

CH CH CH2 + m C6H5CH CH2

K2S2O8; 50 C; 8 H2O

...

CH2 CH CH CH2

CH2

CH CH CH2

CH CH2

CH2

CH CH CH2

CH2

CH CH CH2

C6H5

CH CH2

...

C6H5

1,3-

(. . , 1930) 6080 .

, .
, ,
.
-.

1,4-

:
n CH2

C CH CH2

Al(C2H5)3;
TiCl4

...

70 - 100 C

CH2

C C

CH3

CH2

CH2

CH3

C C

CH2
H

CH2

C C

CH2

...

n CH3

,
.
,

,
25000 .
- -,

(- ).

559

560

.
7 . ., 70%
.
7.4.4.

1,3-

,
,
.

1,3-
.
1,3-

,--1,5;

-1,5,9;

1,2-

, . ,
, (-1,5) Ni(COD)2 1,3

-1,5,9 (. , 1957):
CH2
3

CH

Ni(COD)2; 80 C

CH

CH2
(85%)
-,
-,
-

(6,4%)
-,
-,
-

-,-,-

(8,6%)
-,
-,
-

-1,5,9

95-97% ,
.

560

561

, :

+ Ni0

Ni

Ni

-1,5,9

.
:

+
[Ni0]
Ni

Ni

Ni

Ni

Ni

Ni

, -,
(0). - ,

561

562

;
90 .
-1,5,9
(0).
-,-,--1,5,9,

,
(C2H5)2AlCl TiCl4:

(C2H5)2AlCl; TiCl4

40 C; 1

-, -, -

,
,
.
. Ni(COD)2 (-2) 85%- 1,2 -, --1,5 2:3:
Ni(COD)2; P

C 6H 4

C 6H5)3

50 C; , 5
2

80100 1,2-

-,

--1,5,

.
96%. -,--1,5
.

. Ni(COD)2
4- :

562

563

Ni(COD)2; P (-C6H11)

50 C; , 3
(40%)

(41%)

1,3-
.
.
Ni(COD)2,
-, --1,5 -1,4,9:
+

Ni(COD)2

20 C; 20
(80%)

(20%)

[2,2,1]--2,5:

Ni(COD)2; (C2H5)2AlCl

-1,4:
(C4H9)3Al; TiCl4

-, -, --1,4,7:
R
RC CR +

Ni(COD)2; P(C6H5)3
; 20 C

563

564

,

:
(CH2)10

C
(CH2)10

Ni(COD)2; 40 C

C6H4

C6H5)3

O
H2

1) O3

Pd/C

2) (C6H5)3P

5-:
2HC

Ni(COD)2; P(C4H9)3; 25 C

CH +

,

-, -
.
,
(. 24).

.

.

7.5.
1,2-
. .
.
:

564

565

sp
C

sp2
C

sp2
C

H
H

sp2-
, , . sp-,
.
-
- -

, - :

, (1) (2)
. -2,3 (1,3-)
, ,
, (. . 8):
H

CH3

C
CH3

H3C

(S)-1,3-

CH3
H

(R)-1,3-

-, -

R1
C
H

R1

R1

R2

R1

R1

R2

R1
C C C

565

R2

566

R1

R2

R2

R1

R1

C C C
R2

R1
C C

C
R2

. .
- 1874 .,
. - 1935 .,
. .
-- 1,3--1---3-
:
C6H5

C6H5
C6H5

C C

C10H7-

C6H5

C10H7

C C

O C

C10H7-
OCH2COOH

--
D-10- :
C10H7
C10H7-
C CH C
C6H5
C6H5
OH

D--10-

C10H7
C6H5
D

C6H5
C

C C
C10H7-

20 =351 ( )

160
,
- (. . 8).
,
.

7.5.1.

2,3- :

566

567

CH2

C CH2Cl + Zn

CH3COOC4H9; 80 C

Cl

CH2

C CH2
(98%)

98%,
.

.

:
Cl

PCl5

CD3CCD3

CD3CCl2CD3 + CD3C CD2

Cl2 SbCl5

CD2

Zn

C CD2

CD2ClCCl2CD2Cl

CH3COOC4H9; 80 C

(60%)

.

. -
- :
H

Br
C

CH3CH2CH2

CH3ONa; 80 C

C
CH2CH2CH3

CH3OH - (1 : 4)

CH3CH2CH2CH C CHCH2CH3
(85%)

-4--4

2-

(.

10)

-3,4 85%.
- - HBr 1:1500,
.. -. -4 -
-4:

567

568

H
C

CH3CH2CH2

CH2CH2CH3

CH3ONa; 80 C
CH3OH - (1 : 4)

Br

CH3CH2CH2

C C CH2CH2CH3
(78%)

Z- 2--1- KF .
-O2N C6H5

CH3

KF

-O2N C6H4

; 100

Br

CH C

CH2

Z-

-O2N C6H5

Br
C

KF

CH3

-O2N C6H4

; 100

CH C

CH3

(94%)

Z-

, :
(C6H5)2CH CH C(C6H5)2

1) Br2; CHCl3; 0
2) KOH; C2H5OH; 80

1,1,3,3-

(C6H5)2C

C C(C6H5)2
(68%)

1,1-:
Ar2CHBr + Ar2C

CH2

CH3COOH; 110

Ar2CH CH CAr2

(60-70%)

, (. , 1958).

(. 5):

568

569

H3C

H
C

C
(CH2)3CH3

CH3Li

+ CHBr3

(CH3)3COK

H3C
H C

Br

Br

H
(CH2)3CH3

(CH3)3COH

CH3CH C CHC4H9

; -60

(88%)

,
, :
Br
CH2

:CBr2

Br
CH3Li
; -60

C CH2
(79%)

Br
Br

CH3Li
; -60

CH2

C CH
(81%)

(CH2)n

(CH2)n

HC

Br

Br

Br

Br

CH3Li
; -60

(CH2)n

CH

HC

CH
(CH2)n

,
, .

, 1,3-
1,2-, :
R1CH CH CH CHR2

Al2O3 (COOH)2
t

OH
R1CH C CH CHR2 + R1CH CH CH CHR2 + H2O

569

570

,
.
1,3--1,3-(-) (1935 .).

- ( ).

2 . ,
,
450 :
(CH3)2C

C O

450 ,

(CH3)2C C O

(CH3)2C C C(CH3)2 + H2O

(94%)

:
O C O
C
250 - 280

+ CO2

,
, , , 2.
-
, ,
.
- (. . 6)
,

35%, :
CH3CH2CH2C

CH

KOH; C2H5OH; 175

KOH; C2H5OH; 175

CH3CH2C CCH3
(95%)

570

CH3CH2CH C CH2

H = - 4 /

571

-
,

:
Al2O3 (.)

C6H5C C CH(C6H5)2

C6H5CH C C(C6H5)2
(83%)

.

- ,
- .
.
-1
30:1 100:1, :
C3H7CH C

CH + C3H7CH C

CHCl

Cl

Zn(Cu)

C3H7CH2

C2H5OH; 80

C CH + C3H7CH C

(3%)

CH2

(97%)

.
,

SN2,

:
HC

CH2

RCH C CH2 + RCH2

CH + MgBr2

Br
R

Mg
Br

.
:

571

572

(CH3)2C

C C

CH3 + CH3MgBr

; 0

(CH3)2C

C C(CH3)2 + (CH3)3C
(63%)

Cl

C CH3 + MgBrCl

(24%)

: ,
, .
, ,

. ,
RMgX FeCl3 CoCl3
.
1,3-, 1,1,3 1,1,3,3- -
,

2060 :
CH3
+ [(-C4H9)2Cu]2 Li

; - 60

C
-C4H9

(75%)

OCOCH3
C

+ [(H3)2Cu]2 Li

; - 60

CH

CHCH3

(75%)

.
( N-
RNHCOOH).
.

572

573

RCH C CH + C10H7

CH N C O

OH

CH3

C10H7

CH NH C O CH C
CH3

CH

C C C

; - 20

R1

[R21 Cu] Li

:
H

SO2CH3

+ [R21 Cu] Li

C
R

C CH

R-

S-

R1

:
CH3

H
C

[(H3)2Cu]2 Li
; -5

Br

CH3

H
C

R
(87%)

C
CH3

1,3-
.
,
30 :
CH3

C C

CH CH2 + CH3CH2Li

1) ; -50
2) H2O; 0

CH3CH C CHCH2CH2CH3 + LiOH

(72%)

(. . 16)
:

573

574

(C6H5)2C C O + (CH3)2C

P(C6H5)3

; 0

(C6H5)2C
H3C

C O
C

P(C6H5)3

CH3
150

(C6H5)2C

C C(CH3)2 + (C6H5)3PO
(64%)

7.5.2.
,

. 1,2-

.
.
.
.
.
7.5.2..

, ,
:
RCH C CH2 + 2H2

Pt
C2H5OH

RCH2CH2CH3

. , , -2,3-
, , , -
:
CH2

C CHCOOH + H2

Pd/CaCO3
C2H5OH

574

H
C

CH3

C
COOH

575

-:
CH
Pd/BaSO4

C + H2

(CH2)n

C2H5OH

CH

CH
(CH2)n+1

CH

n = 12 - 20

:
(CH3)2C

C CHCH3

Na
. NH3; -78

(CH3)2CH CH CHCH3 + (CH3)2C

(48%) (34%) -

CHCH2CH3
(18%)

,
, .

, .
, KMnO4
:
R'2C

C CR''2

KMnO4
H2O

R'2C C CR''2

R'C O + R''2C O + CO2

OH OH

.
2,
:
R'CH C CHR''

1) O3; CH2Cl2; -78

2) (C6H5)3P

R'CHO + R''CHO + CO2

7.5.2..

575

576

,
.
(. 6),
,
- ,
- -, :
CH2

C CH2 + H

CH3

C CH2

:
CH2

C CH2 + H

CH2

C CH2

-.

ab initio ,
, , , ,
, . HCl, HBr HI
,
:
CH2

C CH2 + HX

CH3

C CH2

HX

CH3CX2CH3

DCl
:
CH2

C CH2 + DCl

CH2D C CH2
Cl

576

DCl

CH2DCCl2CH2D

577

, -
.
1,2- 2,3- HCl 200 4000
, ,
.

, :
C6H5

CH C

(CH3)2C

CH2 + HCl
CH2 + HBr

CH3COOH

CH3COOH

C6H5CH CH CH2Cl
(CH3)2C

CH CH2Br

sp-
.
, -,
:
(CH3)2C

C CH2 + H

(CH3)2C

CH CH2

(CH3)2C

(CH3)2C

-,

(CH3)2C

Br

CH

CH2

Br
Br

CH CH2

Br

CH CH2Br

, -
- .

-, , -
.
SN1- (. 9),
-, -
.

.
577

578

, 1,3-,
1,1- 1,1,3,3-
FSO3HSbF5 78 sp-
:
(CH3)2C C C(CH3)2 + FSO 3H

SOClF - SBF4; -78

(CH3)2C

CH C(CH3)2
FSO 3

90

(CH3)2C

CH

C(CH3)2

FSO 3

2,3-.
, ,
1,2,2,3-:
CH2

C CH2 + Br2

KBr
CH3COOH

Br

CH2

CH2

Br

Br2; KBrO3
CH3COOH

BrCH2CBr2CH2Br

, , ClBr Il
,
-.
:
CH2

C CH2 + Br2

BrCH2

C CH2
Br

Br

BrCH2

C CH2
Br

(1-, 1,1-- 1,3-)

sp- ,
-
:

578

579

Br
(CH3)2C

C CH2 + Br2

(CH3)2C

CH2Cl2; - 30

C CH2
Br

Br

Br
(CH3)2C

Br
- 30

C CH2

;
CH2Cl2; +20

(CH3)2C

CH2

Br

Br
Br
Br ,

(CH3)2C

C CH2Br

, 3-1,2, ( 30 )
, +20
1,2--3--2.
,
-
.
.

RS+Cl

, RS+
sp- , (1) (3)
:
R
CH2

C CH2 + RSCl

SR

H2C

CH2

Cl

ClCH2

CH2

Cl

, -,
() ,
.
SN2- - .

579

580

, RSCl
.

:
C6H5

S
CH3CH2CH C CH2 + C6H5SCl CH Cl ; 20
2 2

CH3CH2CH C CH2 + CH3CH2CH C CH2Cl

Cl

SC6H5

(68%)

(32%)

,
:

1,2-
. (Hg(OAc))+

- :
NO 2
H
C6H5CH C

CH2 + O2N

SCl

CH2Cl

CH3COOH; 20

NO 2

C6H5

NO2

(86%)

CH2

C CHCOOC2H5 + C6H5SBr

CH2Cl2

BrCH2

C CHCOOC2H5
SC6H5

1,1-

(3-

-1,2) R2C=C=CH2
:
CH2

C CH2 + Hg(OAc)2

CH3OH; 20

AcO Hg

OCH3
AcO Hg

CH2

CH2

HgOAc

OCH3

580

CH2

C CH2
OCH3

Hg(OAc)2
CH3OH

581

(. . 5)
:
HgOAc
(CH3)2C

CH2 + Hg(OAC)2

(CH3)2C

CH3OH; 20

C CH2

OCH3

,
. 1,3 (2,3-) 1,2-
. +

+N-

.
1,3-
, :
E

E
-

CH3

C C C

CH3

(R)- 1,3-
- - 3--4-2 83:17%,

-:

581

582

CH3

C C

CH3
H

Hg(OAc)2 CH3OH

OAc
CH3

Hg
C C

C CH3
H

CH3

OAc
C C

CH3
C H

Hg

OAc

OAc
CH3OH

CH3

HgOAc
C

C
H

H
CH3

CH3
OCH3

C
C C

OCH3
CH3

HgOAc

- (83%)

- (83%)

NaCl

CH3

HgCl
C

+
C

C
CH3
OCH3

CH3

C
C

OCH3
CH3

HgCl

:
CH3
H

HgCl
C

C CH3
CH3O H

NaBH4
CH3OH

CH3
H

H
C

C CH3
CH3O H

H2; Pt

CH3CH2CH2

CH3

CH3O H

, (R)-1,3-
-
.
(R)-1,3- Cl4
-- 3--4--2-

(83 17%), , ..
:

582

583

CH3

C C

CH3
H

Br2 CCl4

CH3

Br
C

Br

CH3

+ CH3
C H
C CH3
C C
Br H
Br
H
-

7.5.3..

,
.
(HBr, H2S, RSH, CCl4, CBr4, CF3I .),
.

.
,
:
CH2

C CH2 + CCl3Br

CCl3CH2

C CH2 (88%)
Br

CH2

C CH2 + CF3I

CF3CH2

C CH2 (96%)
I

CH2

C CH2 + C6H5SH

C6H5SCH2 CH CH2 + CH3

CH2

SC6H5
(80%)

HBr

(20%)

,
1:1.

583

584

CH2

C CH2 + HBr

h
; - 78

BrCH2

CH CH2 + CH3

CH2

Br
(52%)

(48%)

, :
(CH3)2C

CH2 + C2H5SH

(CH3)2C

CH3

(89%)

SC2H5

(CH3)2C C CHCH3 + (CH3)2SnH

(CH3)2C

CH2CH3

Sn(CH3)2

,
,
.
7.5.2..

,
.
(. 25) [2+2], [2+4]
[2+0]-.
[2+2]-

1,2- 1,3-,
:
CH2
2CH2

C CH2

CH2
+

CH2

H2C

t = 110

(100%)

(0%)

t = 170

(65%)

(36%)

584

585

, ,
1,2- 1,3, :
Cl
Cl
C

Cl
(100%)

C6H5

Cl
C C C
H

C6H5

CHCl

C6H5
80

COOC2H5

Cl
Cl

COOC2H5

Cl

Cl

Cl

C6H5
C6H5

Cl

COOC2H5
CHCl

C6H5
C6H5
H

C6H5
(45%)

CHCl

Cl

(55%)

C6H5

C6H5

1,2-:
C

130

(CH2)7

(CH2)7

1,2-,

, .

.
.
[2+2]- ,
.
:
CH2
CH2

C CH2 + CH2

CH CN

t
NC (60%)

585

586

CH2
CH2

C CH2 + CH2

CH COOCH3

CH3OOC (60%)

[2+2]-

:
F

CH2
CH2

C CH2 + CF2

CF2

(30%)

CF2

F
F

CF2

(12%)

[2+2]-
,
:

[4+2]-
,

CH2

C CH2 +

CH2

200
(48%)

586

587

Cl
Cl
CH2

Cl

C CH2 +

Cl

Cl

CH2

150

Cl

Cl

Cl

Cl

Cl

Cl

Cl

(76%)

CH2

C CH2 + (CH3)2C CH CH C(CH3)2

H3C

CH3

H3C

CH3

CH2

200

(37%)

[2+0]- (. . 25).
,
-
, -
.
,
:2 :2 [2,2].

CH2

:CH2

C CH2 + :CH2

[2,2]-

6070%- .
ICH2ZnI,
,
[2,2]- :

587

588

-C4H9CH C CH2 + Zn(Cu) + CH2I2

; 36

-C4H9

CH2

-C4H9

(2%)

(CH3)2C

H3C
H3C

; 36

CH2 + Zn(Cu) + CH2I2

(98%)

(100%)

.
, :

(CH3)2C C CH2 + N N CH COOC2H5 ; 90

CH3

H3C
H3C

CH2

+ H3C

COOC2H5

COOC2H5

(96%)

(4%)

:
Br

(CH3)2C

C CHCH3 + :CBr2

(CH3)3OK
CH3Br - C6H14; - 10

Br

CH3
CH3 (78%)

CHCH3

CHCl3 ( CHBr3)

.
,
:
C6H5C C CH2 + CHCl3 + (CH3)3COK

C6H5

CH2

C6H14; 0 - 20

Cl

588

Cl

589

Cl

(CH3)2C

C C(CH3)2 + CHCl3 + NaOH

Cl

H3C
H3C

(C2H5)3NCH2C6H5 Cl
(CHCl3 - H2O); 40

CH3
CH3
Cl

Cl
(90%)

7.5.3.

1,2,3-

1,2,3,4-

:
H3C
H

CHCH3

2CH3Li
; - 60

Br

Br
Br

Br

H3C
H

CH3
H
Br

CH3CH C C CHCH3

4CH3Li
; - 60

CH3CH C C C CHCH3

Br

, ,
.

Z-, E- (n
), (n ).
Y
; X Y
, , .. :

589

590

X
C

C
n Y

Z-, E- R-, S-. , =65- Y=(CH3)3C-

62,15 / n=1 45,1 /

(n=2), 26,3 / (n=3), 25,1 / (n=4) 19,1 / (n=5).

590

591
8

8.1. ................................................................................................................................. 591
8.2. ........................................................ 593

8.2.1. .................................................................................................... 593

8.2.1.. .................................................................................. 594
8.2.1.. .......................................................... 596
8.2.1.. ................................................... 601
8.2.2. ......................................................................................................... 602
8.2.2.. ....................................................................................... 603
8.2.2.. .................................................................. 607
8.2.2.. ........................................................ 608
8.2.2.. ......................................................................................................... 609
8.2.2.. .................................................................... 614
8.3. ............................................................................. 618

8.3.1. .............................................................. 620

8.3.2. ............................................................................................................... 622
8.3.3. -- .................................................................................. 623
8.3.4. .................................................... 632
8.3.5. ......................................................................................... 635
8.4. ............................................................... 639

8.4.1. ...................................................................... 639

8.4.1.. .................................................................................. 639
8.4.1.. .......................................................... 640
8.4.2. ................................................................. 640
8.4.2.. ................................................................................................. 640
8.4.2.. .... 643
8.5. ................................................................... 645

8.5.1. ................................................................................. 646

8.5.2. ................................................................................ 649
8.5.3. ............................................................................................ 649
8.5.4. ........................................................................................ 649
8.5.5. ............................................................................... 650
8.6. ................................................................ 650

8.6.1. , ....................... 652

8.6.2. ............................................................ 660
8.6.2.. ........................................ 660
8.6.2.. ........................................... 665
8.6.3. = ......................................................................... 668
8.6.4. ........................................................................ 670
8.6.5. ............................................................................................ 670
8.6.6. "" ...................................................................... 671
8.6.7. ..................... 673
8.6.8. ............................................................................................... 674

8.1.

591

592

- . - ;
, ,
,
: , , .

. (..
) .
, :
.
.2
. ,
, ,
, .. , (..
) . , NH3
( ),
().
,
(), () .
, - . ,
, , (
). , 7 , 3,5 .
,
- 70% .
, , ,
.
,
,
, ,
..
, , , ,
(. 8.2.2.).
, .
- ,
,
. , , - , (.5).
,
, .

592

593

8.2.
( . - ) XIX .
. ,
,
. 1970-
.
XIX .; .,
., ., ., ..

8.2.1.
- (, ,
)
().
1811 . .
. 1815 . . (),
, . . ,
, ,

( , .. )

( ) .
(l)
() :

= [] . l .

(8.1)

[] .
,
.
.
( ).
: (. 8.2.1.),

,
( = 0).
.

.

593

594

8.2.1..
.
,
(, ). ,
(, , , ).
, ,
, .
- ;

.
(
).

.

.
, ;
, . (
, , ).
, c ,
.
( ; . 8.2.2.), c
. c
.
, 3
, 4,
2Y ,
XYZ (XYZ) . c,
.

()

-1,2-

() c, .. (2),
, .. .

594

595

H
Br

Cl

H
Cl
F

Cl
F

Br

Cl
H

H
H

C2
H

Cl

H
H

Cl

H
H

.
.

.
.

,
. , c -1,2-
(), , 2-
1-2 ( ),
, .
:

Cl

Cl

H
H

H
Cl

Cl

.
.

H
H

, c
(. 8.2.2), c,
. , ,
. ,
, ..
. ,
, ,
, , , ,
.
( ,
).
(.. ).
( ).
([] (1))
: , .

, . ,

595

596
(, ,
) .
, ,
.
,
. ,
;
, ..
,
() , ()
,
(. 8.6).
, ,
, ..
. .
,
, ,
, , , . ,
204-206, (+) (-) - 170.
6,7 , .

8.2.1..

, .

() , - .
: ?
1823 .

.
, ,
, .

() ,
() ()

(. 8.1.).
,
. . 8.1.- ,

596

597
1,2,3,4 5. ( ..
). 1

, 2 , (
z). 3
, 4 ,
, .. ,
.
(. 8.1.), -
1,3 5 , 2 4 .
1 5

z ()
H
z
x

()

5
4
3

()

2
5

1
4
3
2

.4

.2

()

1
. 8.1. () (), ()
() - (
). () - () (),
.

597

598
(.8.1.).
,
( ),
.
.
,
(..
). ,
, . ,
,
. ,
.
(. 8.2.).
,

.
,
(. 8.2.). ,

( ) (. 8.2.).

598

599

Z
X

+1
14-

E-

4-

4+

4+
3-

E+

2+

3+

2-

33+
()

()

n+ < n-

+ <

()

n+ < n-

+ <

.8.2. () - ,
() - , () . 1,2,3,4 . 1
. "" , "" ""
.
:

= (l/)(n+ + n-)

(8.2)

l - , - , n+ n- -
-

. ,

.

().

599

600

(). (. 2),

= (l/)(+ - -)
+ - - . . 1911 .
. ;
. , ..

() .
1928 . .
. .

,
.
.
. - .
,
.
- .
, J = 1/2, J = 1. ( ,
, , -
, ). ,
J (2J + 1) ,
, .. .
, , ..
(+1 -1). ,
: .

, , () ,
- () . ,
.
,
.

( ) . -

.
-
, .

600

601
,
. ,
, ,
, .
, , ,
. ,
,
, , ,
.
, , .
(
) , .

8.2.1..
(8.1) (8.2)
, .
, ( ) .
. ([]t).
[]D , , D , .. 589 ( ).
[]t. []t,
100.
,
. , ..
(8.1).
[] ,
. ,
,
.

(.8.3). - -
, , . .8.3
.
( ),
. - .
-,
.
(. 8.4).

601

602

8.2.2.
: ,
?
:

. ,
,

.
.8.3. -, (
-).
, - ,
.
, .

602

603

8.2.2..
, ,
, , .
, ,
(1200), , .
.
, ,
.
, , ,
. ,
,
- ,
. .
.
,
.

, Cn, n - ,
, 2/n ,
, - (n),

(), , ,
-

(i)

().
n, ,
(Sn), , i
. ,
, .. ,
.

: .
. 1,
3600 . ,
1 (1 ). 2, 3, - 3, - 4.

603

604

2/3

2/2

2/4
H

C
Cl

Cl

H
C2

C3

H
C3

C3

C3

Cl
Cl

Pt

Cl
Cl

C4

. S1
(S1 ).
. - (Sn)
2/n ,
. , 1,2,3,4

S4:

2/4

2/4
H

CH3

H
H
C

CH3

CH3

H
C
H

CH3
S4

S4

1,2--1,2- S2, -.
S2 ,
- (S2 i)

604

605

Cl F

S2

C
H

2/2

Cl F

H
C

C
i

F Cl

F Cl

. ,
, .
.
,
. ,
. 8.1.
8.1

E C1

CS

S1

IV V

Ci

S2 i

Cl F

H
C

C
H

F Cl

Cn

Cn

VI VII R H (C3)

Sn

Sn + Cn/2

VIII (S4)

nv

S n + n v

H2O

(C2v),

NH3

(C3v),

(v),

(3v)
VI R = H (3v)
3

nh

Cn + 1h

VII R = H

Dn

Cn + nC2Cn

IX X (D2)

Dnd

Cn + nC2Cn + nv

Dnh

Cn + nC2Cn + nv + n

(D6h); 1,3,5-- (D3h)

(Dh)

Td

4C3 + 3C2 + 6S4 + 6

(, )

Oh

3C4+ 4C3 +6C2 + i + 9

Ih

605

606
1 1, s, Ci,
, . 2
. Cn , Cnv
n n, Cn, nh
h, n. Sn,
- n
n/2 (C2 S4, C3 S6 ..). n Sn
. S1 S2 i. 3
n n , n.
. , Dn,
v () - Dnd,

h, Dnh. 4 ,
. .
(Td), (Oh), (Ih).
, Kh,
.
, Td .
, CHCl3 ,
; C3v ( ), Td.

606

607

H 3C

N CH3

H
H

H 3C

R
R

H 3C

VI

IV (C1)
(C1)

R
H)

C3 (R

C3v (R = H)
R

H 3C

H 3C

N H 3C

H
H

CH3

VII
R

H
(C1)

V (C1)

H)
C3 (R
C3h (R = H)

R
H

CH3

H 3C
CH3

H
VIII (S4)

CH3

(S4)

H 2C

CH2
C2

H
H

H 3C
CH3

N CH3

C2

R
H 2C
O

CH3

H
IX (D2)

R
(D2)

CH2
X (D2)

8.2.2..
:
, ? ,
,
? ,
, 1, ,
( 1, .. 1 ). , , ,
() (i) ,

607

608
( ), 1800 (
). , - (Sn)
, . , ,
n Dn.

:
, Sn .

, ,
, , . S1 S2 i,
, , i.
, i, , Sn, .
1,3,5,7- (XI), ,
, - S4. .
CH3
CH3

CH3

CH3
CH3

CH3
CH3

CH3

CH3
CH3

XI

CH3

CH3

XI

IV, V, VII IX. IV V ( C1),
VII ( D2). .
, . VIII
S4, .. , .

8.2.2..
,
.
-
. ,
. 1971 .
1) ,
: (v ( ), Dh ( ), Ih, Oh, Td ( 4, . 8.1).
. , v Dh
, H-CC-Cl (v), H-CC-H, Cl-CC-Cl (Dh). ..
2) ,
n. , (3).

608

609
, i
. , i,
, - s.
( ), C1.
3) n, .. n. ,
- S2n, . ,
, , , i , Sn, n . S2n , , S2n
, (4).
4) n , , n.
, Dn, Dnh Dnd.
(5). c , n, Cnh,
Cnv. (6).
5) h, ,
Dnh. , n
d (.. , ,
). d, h,
Dn.
6) h, Cnh. h
, n v ( ).
nv. v, h,
n.
, 8.1.

8.2.2..
, , ,
1.

(XII).

CH3
CH3
H

COOH
COOH
Br

Br
XIII

XII

609

610

8.1

Cn

Cs

Ci

Cn

nd

Cnh

Cnv

Sn

nv

Ih

Cn

nC2Cn

C1

Oh

Td

S2n ( S2n i)

Dn

Dnh

Dnd

,
, ; , XIII
. XII XIII ,
.
, Td C1,
. XIII
, - , ,
( ). -
.

610

611
, Cn Dn.
.

C3
NH

C2

NH

C2
S
S
C3

C2

(CH2)6

(CH2)6

C2

C2

D2
. ,
, ,
. ,

.
, .

, :

611

612

, .
sp- - p-,
p- ,
. ,
- S4,
== .

b
a

C
C

b
2

C
H

(2)

,
:

H3 C
H 3C

H
C

C
H

H H 3C

H 3C
H

C
H

H
C

C
CH3

, , , 1,2,3-:

, --.

612

613
, XIV .

(CH3)3C
C

Ar

C(CH3)3

Ar
XIV

(Ar= n-ClC6H4)

, :

CH3

NH2

CH3

NH2

, -,
- ,
. ,
, ;
, :

NO2

NO2

COOH

COOH

NO2

COOH

NO2

COOH

, ,
, .

-. ,
-2,2- (XV). XVI
, , ,
( 9 . 250).

613

614

SO3H

NO2

SO3H

OCH3

COOH
XV I

XV

, , .
, ,
, . -

(XVII).

(XVIII), XIX XX.

X

X
Y

COOH

OC
Fe

Fe

OC
OC

HOOC
(CH2)8

Cr

(CH2)10

CH3 Br
O

(XVII)

(XVIII)

(XIX)

(XX)

.
, . ,
-
.

8.2.2..
, , ,
,
.

614

615
, XXI ,
. XXI
.
CH2

CH2

C
C

CH2

CH2

CH2
CH2

CH2

CH2

CH2
CH2

CH2

CH2
O

CH2

CH2

CH2

CH2

CH2

CH2

CH2
CH2

CH2

CH2

CH2
(XXI)
CH2

, 60 (XXII),
, .

(XXII)

. ,
, .
, ;

.

615

616

c
d

c
d

[3]

[2]
A

,
. .

X +X

X +X

. -
,
. .

616

617

(CH2)32

+ ArC

(CH2)32

(CH2)13

+ HO

HO

H (2-

CAr3

(CH2)13

OH

Ar3COH

(CH2)13

OH

(CH2)13

O CAr3

(CH2)32

Ar3CO
(CH2)32

1%

(Ar = (CH3)3 C

)
O(CH2CH2O)8

OH
HO(CH2CH2O)8H

+
O(CH2CH2O)8

OH

-400

()

B + ArPh2C

O(CH2CH2O)8
(Ar = Br

CPh2Ar

CH2

617

618

Ph

Ph
Ph

O(CH2CH2O)8

(CH2CH2O)8
O(CH2CH2O)8

;
18,5%

CH2

CH2

Br

Br

-ZnBr2

OCPh

Zn/Cu

CH2

CH2

C Ph2

O(CH2CH2O)8
(CH2CH2O)8

O(CH2CH2O)8

14%

8.3.

,
.
, -
. ,
. .4
, .
- :
.
.

618

619

.
.24; .4.
- ,
, . -
.

() . ,
.

( ).

-,

ClCF

HCBr. ,
900, = 0 - ,
. = 1800
. , = 2700
, .
00 < < 1800 ,
1800 < < 3600.

. , .. ,

= 00 = 1800. , - , .

= 900
F

Br

1800

Cl

Cl
F

Br

Br

Cl

00

2700

Cl
F

Br

109,50 900, .

619

620

Cl

Cl

Br

Br

Cl

H
F

Br

- ,
.
, .

, .
:

H
Br

Cl
F

Cl

H
Cl

F
Br

Br

Cl
H

Cl

Br

Br

. ,
.
.
,
,
, ,

, .

, .

8.3.1.

620

621
.. ..- 1874 . ,
, ,
, .
.
, .. ,
.
,
( ), .
.
:
.
XIX - XX
. -
.
, ,
. (+) -
XXIII D (dextriogyrus - ), () - XXIV - L (laevogyrus - ). ,
. ,
HgO (+)- (-)- .
, ,
, (-)- D - .

HO

HO

HOCH2
H

OH

H
(XXIV)

(XXIII)
D -

CH2OH

HO

L -

+[]

-[]

621

622

OOH

HO
HgO

HOCH2

HOCH2

OH

OH

(+)-D -

(-)-D -

, . D L - ,
, , .

8.3.2.

. 1891 . .
, .
,
, , , ,
, - . :

CHO

CHO
HOH2C
CH2OH

OH
H

OH
H

, 12
. , ,
, ,
. .
900, 1800 .

622

623

CHO
OH

HOCH2

OH

OHC

CH2OH

HO

H
CH2OH

CHO

. -
.

CHO
HOCH2

CHO

CHO

OH

HO

OH

CH2OH

CH2OH

HO

CHO

CHO

CHO
H

H
CH2OH

L -

OH

CH2OH HOCH2

HO
H

CH2OH

CHO

OH

D -

,
, (, ).
.

8.3.3. --

,
.
, ..
D- L- ,
( . 8.5). ,
, ,
,

623

624
. ,
D - L - . , D , , ,
- ,

(XXV).
, XXV D - .

CHO
H

OH
CH2OH

OOCH3

COOH
HgO

OH
CH2OH

CH2N2

OH

OOCH3

[O]

CH2OH

OH

CH3CHN2

COOH
OOCH3
H

OH
COOC2H5
XXV

COOC2H5
CH3CHN2

OH
CH2OH

[O]

COOC2H5
H

OH
COOH

CH2N2

COOC2H5
H

OH
COOCH3
XXVI

, ,
XXVI, D-.
XXV XXVI ; .. D-
L- . , , , CO2Et
CO2Me, "".
, , 1951 .

, 1966 ,
, R,S- --
() .
D,L- (, ,
).
R- S-, .
Xabcd, .
,
(. ), .. 1>2>3>4.

624

625

( 4). 1

2 3 ,
R ( rectus - )
- S (sinister - ).

3
2

(R)

(S)

,
.
1)
. ( ),
. "" - .
, : < H < D < T < Li < B < C < N
< O < F < Si < P <S < Cl <Br < I. :

1
OH

4
H
T

4
F

(S)

C
D

I
Cl

2
Br
Cl 3

(R)

2) ,
, ,
, , . ,
XXVII 2 (3)2
, 2, ,
. 2 , ,
, (3)2 - .
, ..

625

626

1
Br
4
H

Cl

3
(CH3)2CH

2
CH2OH

(R)

XXVII
,
, , ,
- . ,

.
,
.

. , CCl3 > CHCl2 > CH2Cl.
3) , , , 4.
(, , , ), ,
4-n ( n - ) -

,
.
, .
, =
, ,
-. -=2, -, , - -65. .

626

627

000

000

000

00

000

000

00

000
000
C

CH

000

000 000
000

C6H5

000

000

(,,), (,,), (,,), (,,)

(,,). ,
( ), , -=2 - () ,

. -65
. 65 (,,),
(,,), (,,).
(,,), (,,). , 65 , , ..
: > > 65> > =2.

627

628
.
8-2, .
8.2.
--

, =2

10

, SH

69

, NH2

43

, H3

, NH3+

44

, NHCH3

45

, COCH3

36

, SOCH3

71

, NHCOCH3

48

,OSO

66

CH3
, OCOCH3

64

, SO2CH3

72

, CH2C6H5

13

,OSO2

67

CH3
, OCH2C6H5

60

,SCH3

70

, COC6H5

37

,OCH3

58

, NHCOC6H5

49

, COOCH3

30

, OCOC6H5

65

, CH2C(CH3)3

11

-,

50

, NO2

56

, Br

75

, NO

55

-,

16

NHCOOCH2C6H5

27

NO2

CH(CH3)CH3CH3
-,
-, CH2CH2CH2CH3

33

NO2

-,
-, C(CH3)3

24

19
NO2

-,

628

629
42

, C5H11

, CH2 = CH2

15

, CH=CHCH3

18

, H

, CH2CH2CH3

-, C6H13

, CCCH3

29

, OH

57

, CH2CCH

12

62

, SO3H

73

, N(CH3)2

51

-,

COOC(CH3)3

25
CH3

-,
2,4-,

30

34
CH3

NO2

-,
NO2

3,5-,

23

28
CH3

NO2

-,
NO2

, N(C2H5)2

52

, CH2CH(CH3)2

, C(C6H5)3

32

, C6H5

22

, CH(CH3)=CH2

20

, N=NCC6H5

54

, CH(CH3)2

14

, NHC6H5

47

, I

76

, OC6H5

61

, COOH

38

, CHO

35

31

, OCHO

63

+
N(CH3)3

53

CH2CH2CH(CH3)2

CH3

2,6-,

CH3

629

630
26

CH3

3,5-,

, F

68

, Cl

74

, C6H11

17

, CH2CH3

, NHC2H5

46

, CCH

21

, OC2H5

59

, COOC2H5

40

CH3

,
,
, D-
, .
D- , , , (R)-, L (S)-.

CHO
H

OH
CH2OH

D-

4
H

Cl

2
CH2SH

COOH

3
CH2OH

H2N

4
H

CH2SH

(R)-

L-

3
COOH

Cl

NH2

(R)-

L-, (R)-,
.
.
. ,
.

.
. ,
, ,
Z - ( zusammen - ),

630

631
, (entgegen - ). (Z, ) -
.5. (Z, ) - .

1
X

1
X

(E)

(Z)

C
CH3

CH3

(Z)--2

1
CH3
C65
2

Cl

C
1
H

C
H
2

(2,3E),(4,5E)-2--2,4

2
OH
C

1
CH3

2
H

2
CH3

H
C

H
Cl

5
(Z)

H
4

(E)-

Cl

1
CH2OH
2
H

(E)

5--3[2()-]2(Z)-4(Z)--1

,
Z - . (R,S) -
.
, , ,
, ,
, .


. 1,3 - 2,2 -6,6- .

631

632

2
H

COOH
C

1
I

4
H

3
COOH

HOOC
I

4
HOOC

COOH

COOH
1

COOH

COOH
2

(R)-

(S)-

.

.
, ;
, (R)
- , - (S) -, :

OH

OH

CH2OH

HOC

CHO

HOCH2

H
(R)-

(S)-

, ,
, .

8.3.4.
,
(R) - (S) - , : RR, SS, RS
SR:

(R) T

(S) V

(R) X

(S) Z

Y
(RR)-

U
(R) T
(S)Z

Y
(SS)-

632

(S) V

(R)X

(RS)-

(SR)-

633
,
(RR) (SS). ,
(RS) (SR). ,
. - ,
. , (RR)/(RS), (RR)/(SR), (SS)/(RS)
(SS)/(SR). (RR) (SS), (RS) (SR), ,
( ).
: , ,
.
. ,
.

, : (RR)
(SS), , (RS),
(RR) (SS). ,
: -.

HOOC

COOH
C

OH

HO

(C2)

C
COOH

(S,S) -

(Cs)

HOOC

HO

(C2)

OH

HOOC

OH
(R,R) -

COOH
HO

(R,S) -

( - )
- (R,S) - , ,
- ().
-
-, ,
. -
s, .. .
n ,
2n;
-. , ,
. ,

633

634
,
. 2,3,4-
. 2 4 (R) (S),
:

CH3
(S) H

OH

(S) H

OH

HO

(R) H

OH

(R) H

CH3

CH3

CH3

CH3
(S) H

OH
H
OH

OH (R) HO

HO

OH

(S) HO

(R) H

OH
CH3

CH3

CH3

() -

,
. , ..
, ,

. ,
,

.
,
, , ,
- -, .
, .
-
, (Cl Br
) , -. ,
, .

634

635

CH3

CH3

CH3

CH3
Cl

Cl

Cl

Cl

Br

Br

Br

Br

CH3

CH3

CH3

CH3
-

CH3

CH3

CH3

Cl

Cl

Cl

Cl

Cl

Cl

CH3

CH3

CH3
DL -

8.3.5.

, . ,

, ,
:

635

636

CH3

CH3
CH3

CH3

()
H

()

H
H

CH3

- SC

ap

+ SC

CH3

CH3

CH3

H
()

()

H
sp

()

CH3

CH3

CH3

H
()

H3C

H
H

CH3
+ac

-ac

IUPAC :
- (sp), - (sc), - (ac), (ap; - ; - .
clino - ). ,
, .. . , () ()
. , () "" (+sc),
() - (-). () ()
( 0, ..
) +
-. , CH3-C-C=CH2
. , ()
(. ),
() .
,
: 3-.
: (1) ,
( )
. (2) a2bC,
" ", b,
.
2,2,3- +sc. ,

636

637
, : Cl2
l.

CH3

CH3
H

Cl

Cl

Cl

Cl

Cl

Cl
CH3

CH3
+ SC

- SC

.
(+) (-)- ,
.
,
, . ,
, (R, R)-
(S,S)- .
(S,S)- (R,R) , (R,R)-.
, .

CO2H

CO2H

HO

HO

CO2H
OH

OH

CO2H

CO2H

CO2H

HO

HO

(R,R); + SC

CO2H
OH

OH
H

(S,S); ap

(R,R); ap

637

OH
OH

(S,S); - SC

CO2H

OH

(R,R); - SC

HO2C

HO2C

HO

CO2H

(S,S); + SC

CO2H

638
-
S2 (i) ,

(+)

(-)-

, ,
, ..
. , ,
.

HOOC

OH

+ SC

i)

(R,S); ap; (S2

OH
OH

OH

COOH

COO H

HO

HO

COOH

COOH

COOH

- SC
(R,S); C1

- .
, ,
, .. ,
. -
sp-, -
6h ..

C 6h

COOH
COOH
COOH
COOH
H

OH

()

HO
HO

H
H

HO

SP (S1

)
C6h

, ,
. D- L-

638

639
, .. , ,
, .

8.4.
8.4.1.

8.4.1..
,
, - ()
.
(C,H,N,O,F,Cl),
, . ,
, ,
.
,
.
,
, , ,
.
.

.
.
, .

, , ,
.
1951 , ,
- , L-
- ,
(+)- (XXVIII) (-)- (XXIX).

639

640

COOH

COORb
Br

HO
H

OH

H3N

H3C

COONa

C2H5

(XXVIII)

(XXIX)

XXVIII ,
(+)- , ,
, .

. ,

, , .

8.4.1..
1952 -
-2,3- (XXX).
.
, D
.

CH3

H
H3C

XXX
8.4.2.

, .
.

8.4.2..

640

641

,
, ,
.
.


, , .
, ,
, .
, (R)-,
(R)-. , (R)-1--2 2-, , (S)-
, . , H3CH2
(. 8.3.3.) BrCH2, 3.

OH
CH2Br

CH3CH2

OH
CH3

CH3CH2

(R)

(S)

D- (XXXI) .
,
XXXII,
XXXIII. (XXXIV),
, . ,
D- , XXXI.

COOH

CHO

COOH

COOH

OH

OH

OH

HO

HO
HO
H

H
H
OH

HO
HO
H

H
H
OH

H
H
H

OH
OH
OH

HO

CH2OH
(XXXI)

COOH

COOH

(XXXII)

(XXXIII)

OH
COOH
(XXXIV)

L- ,
. ,

641

642
( XXXI
XXXII), .
(+)- (+)-(R) , .

COOH
H

COOCH3

OH

HO

COOCH3

OAc SOCl2 H

HO

COOH

COOCH3

COOCH3
H

OH
CH2

OH

Zn
H

OH

OH

CH2

COOCH3

COOCH3
NaOBr

OAc
CHCl

(+)-

NH3

COOCH3

COOCH3

COOH
HNO2

CH2NH2

OH

CHO
HgO

OH

CH2OH

CONH2

CH2OH
(R)-(+)-

, . , SN2
() (..9 ).
(+)-
(S)-(+)-.

COOH
HO

H
CH3

NaOH
H
S N2

(S)-(+)-

Br
CH3

COOH

COOH

COOH
NaN3
SN 2

(R)-

H H2N

N3

CH3

(S)-

(S)-(+)-

, "" ""

. ,
(
R,S-), "" ""
, .. ,

, :

642

643

C3H7
CH3SO2

C3H7
LiAlD4

O
C2H5
CH3

H5C2
H3C

(S) -

(S) -

. ,
, , .
- , , (S)-, (R)-,
, ,
, (S)-.

8.4.2..

,
, .
( ) .

.

XXXV XXXVI. ,
, .
, -, XXXV
XXXVI (
) .

C8H17
Me
Me

O
Et

Me

Et

(XXXV)

(XXXV)

( )

643

644
- ,
. ,
=,
.

- . , , 1,3-
(XVII) 2
, ,
2- .

Ha
(3,32 ..)
XXXVII

He

(4,07 ..)

- (J) 8
:

HA

HB
0

60

90

120

180

JAB,

3,5

10

, , J .

, . ,
(,

- XXXVIII) 8
-
C=O, OH, NH2 .
. , , -

- (XXXIX).

.. , , ,
.

644

645

(4,7) H3C

CH3 (11,0)

(4,0) H3C

t-Bu

CH3 (4,4)

O
H

Eu/3
OH. . .(Eu)

CH3
(10,5)

t-Bu

(17,6) H

(7,2) H
- (XXXIX)

XXXVIII

CH3
(8,6)

- (XXXIX)

OH
.
.
.
(Eu)

( ,
, ..).
.
, ,
,
.

8.5.

.
, , ,
, ..
.

, (
().
(..).

[]
[]

.. =

- *
+ *

* 100%

* 100%

- , ,
* - .

, ,

645

646
.
.

8.5.1.
.
,
. ,
. , (
) (S)-. (R)- (S), .

(R)
(S)

(S)*

(S)-

(R,S)

(S,S)

(R,S)

(R)

(S,S)

(S)

, , ..
.
. .

, .. -
.

, , , , , ,
, , .
.
, , -. ,
3--2- .

646

647

COOH

COOH
Ph

Ph

Ph

CH2Me2

CH2Me2
(S)

NH2

H
Me

(R)

(S,R) (R,R)

(S,R)-
(R,R)-

: , (-), (),
(-), (XL) .
,
, ,
,
.
,
, , ,

647

648

CO
CH

Cl

OH +

O
CO

Ph

O
S-

HOOC

Ph

CH

Cl

CH

Cl

Ph

C
OOC

1)

2)
+
()

CH

Cl

OH

( )

Ph

, , ,
. , ,
, (,
),

. (XLI),

,
.
-
( ), (R)- -
(XLII).

NO2

NO2

H2SO3H

Cl

(CH2)4

O
Me Me

Pt
O2N

H NO2
N

(XL)

C
CH3

(XLI)

648

COOH

CH3
NH2

Cl

C
Ph

(XLII)

649

8.5.2.
c ,
, , ,
. , , ,
. , ,
.

8.5.3.

270 ( ) :
(+)-, (-)-.
, .
. 1848 . ,
(+)- (-)-.
. ,
, ( ;
- ). ,
([]D20= +62000) .
5--3,3--2,4- (XLIII)
20 400 3
. ,
1,1,- (XLIV). 761500 - .

O
C2H5
C2H5
H3C

N
H

(XLIII)

(XLIV)

8.5.4.

, .

649

650
N-.
N- L- 1000
D-, L D-.

8.5.5.
,
100%- .
, ,
, ,

, , .

8.6.
,
, .
,

. ,
"" .
, -
, :

C6H5CH2COOH + Br2

1. PBr3
2. H2O

C6H5CHCOOH
Br

(R)- (S)- -
(..=0), , ,
,
. ,
. ,

( - )

650

651
2- ,
:

CH3

COOH

1. , -2
+

COO Na

C2H5

2. H3O

C2H5CHC

COOH

CH3
[]D = 0 (.. = 0)

CH3

COOH

C2H5

1. , -2
+

2. H3O

C2H5CHCCOOH

COOH

CH3

[]D = -1,7 (.. = 10%)

(. , 1904).
.
1904 . ,
(-)- (XLV).

CH3
C6H5 C C
O

O
O

1. CH3MgI
+

2. H3O

C 6 H5

COOH (.. ~ 25%)

OH
(XLV)
.

, , ( ,
) , ,
,
(3MgI ) ,
.

.
, .
(1) ,
, (2) (,

651

652
), (3) (4) .
( ) ,
98% (. , . 27),
100%. 100%
.

. ,
,
, ,
.

8.6.1. ,

.
, ,
.
. , 1,3,6,8- (XLVI)
, 1,8 3,6.

C2
O2N

NO2
(XLVI)
NO2

NO2

,
( . - );
Cn (, n 1 n ). XLVI Cn = C2;
:

O
P
Ph

Ph

Ha
H

Ph

O
H

OH

O
O
OH

C3

C2

C2

:
Ph/Ph/Ph

C2

H/H

Ha/Ha H/H

652

OH/OH

653
,
:

Cl
H
CH3

H3C

(Cn )

, ,
- .
, - . ,
1 2 , 1 2 Z
.

F
C2

F
F

(1)

H1
F

H2

(2)
F

H
Z

, 2- Z
.

OH

OH

H 3C

(1)
H1
H2

Z
H

H 3C

OH
(2)
H 3C

H
Z

, 1 2 . ,
.
,
() Sn
(- ). S1 (.8.2.),

653

654
(. ,
8.2.2..):
, ,
S R (.. ).
1

HS

CH3

HR

HR

HS

O
C
HS

HR

H3C

HR

HS

.
(, -),
. ,
,
. ,
- , ,
,

.
, , (XLVII)
. ,
2- (XLVIII), ,
,
.

HOO

COOH

COOH

COOH

CH2

CH2

CO

OH

HOO

OH

CH2

CH2

CD2

CD2

COOH

COOH

COOH
(XLVIII)

(XLVII)

654

655
;
, .
, .
,
, Z
( Z- E- ).

:
3
3

(A)

Cl

Cl

CH3
(B)

CH3

( )

3
H

Cl

CH3

Z, E -

(A)

(B)

.
, :

655

656

H
H

Br
H

O
Cl

( Z
)

,
, . -
. ,
,
.
,
, , " "
. :

656

657

Ox

HOOC

COOH

COOH

CH2

CD2

OH

HO

COOH

CD2

CH2

COOH

COOH

D2

. ,
, .
, - ,
. ,
, .. .
, ,
.
, X2CYZ X , Y, Z
, , Y Z .
Z , , Z = abc, , b - .
, , ,
X X :

Y
a

xA

xA

xA

(A)

()

(B)

X , X - b . X
b, X - . X b , X b. , X X . ,

657

658
, , , ..
, , X
X. ,
X X ,

.

.
. -
.
( ) ().

A
A

C
R

-O

C
R

A
C

,
,
:

658

659

A
O

C
R1

-O

+
R1

R1

. ,
, ,
.

, .

- .

),

. , XLIX ,
.

H 3C

H
C

+
Ph

H3C

659

H
C
Me

(XLIX)

Me

Me

H 3C

H
Ph

Ph

660

, , ,
.

8.6.2.

.

,
. ,
,
.
(, , ..)
, .



=0.

8.6.2..

.
.
, ,
. , 2,2-1,1- (XLIX) ,
,
:

OH

+ LiAlH4

Li

OH

O
O

XLIX

660

H
Al
H

661
XLIX
; :

COOH

Me
H

CH2NMe2
H

NMe2
H

PhCH2NH

Me

OH

CH2Ph

HO

Ph

CH2SH

Ph
("")

,
, "" .
, " " ,

- - ,
.
, " ",
,- L ,
BINAL-H. :

Un

Un

R
Un

(R) - BINAL - H

HO

(S) - BINAL - H

H
Un = , ,

O
O

(S) (.. ~90%

H
Al

OH

(R) (.. 90%)

H
Al

Li
O

OR'

Li
O
R'

(L)

(S) - BINAL - H

(L

661

662
, BINAL-H LI,
OR (R = Alk) .
:

Li

Al

Li

Al

R'

R'

, ,
: ,
.
, , (S)- BINAL-H (LII LIII),
, LII, (S)-
, LIII
- .
Un

(S) (S)

Al
O

Li

Un

(LII)

(S) O

Al
O

O
R

Li
S

(LIII)

S -

, - n,-
(), .
R
LII , -

662

663

, , .

:

DO

OD
Li Al D(OR*)2

C
H

Ph

Ph

Ph

(S) - 83%

(R) - 17%
(R*OH = "")

-3-9-[3.3.1], -N.
, -
80-100%.
BBN
R

CR' +
_

CR'

H3O

CR

OH

OBBN

BBN =

4--, -
. ,
- ,
-.

H
(CH3)3C

H
+

0C
(CH3)3C
B(i-Bu)2 1. -78
2.

H
OH

663

(96%)

664
-.

(CH3)3C

(CH3)3C

LiAlH4

-400C

OH

(95%)

, :

Al

H
OH

O
H3C

OH

C
H

C6H5

CH3

CH3
CH3

(R)-; LiAlH4 72%

LiAlH(OBut)3 82%

.
, ,
(NADH),
,
- . (LIV)
- .
, LIV ,
,
80%:

664

665

H
Ph

COOEt +

CO N

CO N

PhCHCOOEt +
CONH2

CH2Ph

NH

N+

OH

CONH2

CH2Ph

(.. ~80%)

COOH
( )

8.6.2..

.
-, -, -, - . ,
LV
LVI,
1--.

CH2

Me

2 BuLi

-BuH

Me
Bu

CH2OH

PhCHO

Li
O

Li

(LV)

(LVI)

*
PhCHBu
OH

665

666

Li

Ph

O
Mg
O

Ph H
- (1:1)

+
R

Li

-1000

O
C
R2Zn

(-)-DIAB H2O

CH2CH=CMe2

OH
1. RCHO

R
H

RCH

2. H3O

(.. 92%)
R

OH
(.. 98%)
H

Me
C

CH

CH2 (.. 96%)

Me

,
.
(. .16).

,
. , , -

.

,
. ,
, LVII,
, , (

).

,
( ).

666

667

A
O
C
C

(LVII)

M
R
:

H3C

CH3

MeMgX

R
C6H5

R = Me 66%
OH

EtMgX
PhMgX

CH3

R = Et 75%
H

C6H5
CH3

R = Ph 83%

( )
. ,
.
,
.
, -
. ,
,
- . ,
- : LVIII-.
LVIII LVIII
, = , LVIII -
. , ,
.

667

668

O
R

M
O

O
O

A
LVIIIa

LVIII

M
C

LVIII

, , :

(M)
(C)

O
O

C
Ph

C
O

CH3
CH(CH3)2

Me

HO

H
1. MeMgI
2. OH3. Al/Hg

C
Ph

OH

(62%)

O
()

(R)-

8.6.3. =
, = , -

.5.
.

668

669

H3C

H3C

*
BR2
H2O2; OH

R*2 BH
H3C

H3C

CH3

* CH

OH

C2H5
100%-

R* =

(-3)

-3- -3- (R*BH2).

(.8.3).
8.3.

2--1

(%)
R2*BH2

R*BH2

5 - 30

1,5

76 - 98

20 - 24

13

70 - 92

14 - 22

52 - 100

CH3
CH2

-
R

R
CH

CH

-
R

CH

CH
R

(-
-)

.8.3. , R*BH2 -
-,
- R*BH2.
.

669

670

-
(..16).
,
, :

CH2 NO2
Ph

CH

B*

COPh +CH3NO2

CH

Ph

CO Ph (.. 51%)

CHCH2

(B* = ; ).

8.6.4.
-
(.., 1982). N -.
( ) (II)
LIX, 2- ( )
.
---, -
.

COOH

CH3C6H4NH2-
N
CH2Ph

CH2Ph
N-
( )

COCH3

2. H3O

CON

*
CH3CH(OH)CH(NH
2)COOH

Cu
O

Cu(II)

1. H3CHO

N
PhCH2

H2NCH2COOH

CONH

CH3

1. R2NLi

CH2

2. RX
+
3. H3O

(LIX)

*
CH(NH
2)COOH

97-100%.

8.6.5.
, ,
. ,

670

671

, (.. = 2,5%),
. 2- - ( ) ..
12,5%.

CH3
OH

O2
Cu Pd,

(.. 12,5%)
O
1--1,2-

, ,
,
, , :

CH3
CHMgCl + CO2

(+)-CH3CH(OCH3)CH(OCH3)CH3
()

C2H5

(+, -)

HCCOOH

2.

C2H5

CH3

(-)

[(+)

2,3-]

.
, 2.
,
, - .
()
. , -
.

8.6.6. ""
"" ,
,
. ,
?
. ""
, , ,
, , . ,

671

672
(), ""
"" , ""
- .
""
,
. ,
, ..
.

1930- . , -

3(N3)CONMe2

,
( ). 1970- , :

h
313 , 10 .

(.. 0,2%)

,
- .
- .
(LX) LXI.

X
O

(.. 3%)
O

(LX)

(LXI)

"" ,
. ,

672

673
9 (LXII)

CH3C6H4

Br2

CH3C6H4

COC6H4CH3

H
(LXII)

*CH

*
CH

Br

Br

COC6H4CH3

(.. 6%)

8.6.7.

,
(,
; 8.6.2).
, .
,

. , :

R'
R'

CH

OTs

LiAlH4

H
R

-:

,
.
673

674

H
(S)
(S)

O
C

(RO)3P

+ CO2 + (PO)3PS

O
H
(+)-

(R)-(+)-

8.6.8.

.

. ,
,
,
.
,
, , . 27.
,
.
,
, ,
.
, ,
(.. ) .

,

;
, () , , ,
( ).
,
,
1996 . - -2-
CuII (LXIII).
.

674

675

Ph

CH

Ph

CuII - .

CH2 + N2CHCOOEt

COOEt

- (.. ~10%)
PhCHCH3
N

CuII - . =

O
Cu
N

CH3CHPh
(LXIII)
10%,
(.. ) ,
, .. = 94%.
(S)-2,2- (
-1).

C=C, C=0 C=N-
. (.
. 27).
1) (-)

675

676

NEt2

(S) - BINAP - Rh

CHO
NEt2
(R) -; .. = 96 - 99%

(-) -
OH

OH

PPh2

PPh2

PPh2

PPh2

H
OCH3

Ph2
P
Rh
P
Ph2

OCH3
H
ClO4

(R) - BINAP

(S) - BINAP - Rh

(S) - BINAP

2)

676

677

HO

H2

H2

(S) - BINAL - Ru

(R) - BINAL - Ru
R'

R'

OH

R'

(R = Alk, Ar)
R'

, %

CH2CONMe2

96

CH2COSEt

93

CH2COR" (R" = CH3, Ph)

94-100

CH2CH2OH

98

Br
(-)

92
93-96

CH2NMe2
CH2OH

92

COOH
(-)

92
O

Ph2
P

(S) - BINAP - Ru

O
Ru

P
Ph2

O
R = Alk

. , -

(-)-DIAB (R)-
92%.

677

678

O
R2Zn

OH

(-)-DIAB-. H2O

NMe2
(-)-DIAB

=
OH

(-)DIAB LXIV,
C2, . ()-DIAB,
2, . 2
, ..
, 2.

Me2
N

NR2
+

2R2Zn

OH

R
Zn

-2RH

DIAB

Zn
R

N
Me2
(LXIV)

R
N
O

C2
O

Zn
R O
Zn

Zn

i
Zn

O
N

2. :

678

679

1_
(LXIV)
2

Me2
N
+

O
Zn

ArCHO
O

Me2
N

Ph

Ph

O
Zn

R2Zn

R
Zn
R

Me2
N
R2Zn

Zn
-ZnR2

*
CH

Zn
Zn

Ar

Zn
R

Me2
N

H R
R

OZnR

Ph
8.7.

. ,
, .
, :

F
CH3

H3C

CCl3

Cl
Cl

Cl

Cl

e
LXV

: (, b
LXV) , (d ) - . ,
LXV , ,
20 , 10 .
, 10,
.
, 4 6
.

679

680

1
3

3
5

5
4

C4v

D3 h

D3 h
( 3 2
)

( 1 2 )

,
( 5)
,

.
1--2 180 1200, 3--4 120 1800, ..
1 2 , 3
4 - . , ..
900 5.

D3h C4v .

""

, ,
.

680

681

9


9.1. SN1 SN2.............................................. 685
9.2. SN2 ....................................................................................................................... 692

9.2.1. .................................................................................... 692

9.2.2. SN2-................................... 696
9.2.3. ,
SN2-.................................................................................................... 698
9.2.3.. SN2- ....................................................... 699
9.2.3.. ............................................................ 701
9.2.3.. ................................................................... 703
9.2.3.. ............................................................................................. 713
9.2.4. ......................................................................................... 717
9.3. SN1 ....................................................................................................................... 720

9.3.1.
................................................................................................................................ 726
9.3.2. ................................... 736
9.4. ...................... 737

9.4.1. ........................................................................................... 738

9.4.2. .......................................................................................... 740
9.4.3. .................................................................................... 743
9.5. ........................................................................................... 746

9.5.1. ........................................................................................................ 746

9.5.2. - .............................................................. 750
9.6. SN-.................................................................................................... 751

9.6.1. SNI ................................................................................................................... 751

9.6.2. (SN)....................................................................... 753
9.6.3. ......................................................................................... 756
9.7. ................................................................................................................... 763

9.7.1. ................................................................................................. 763

9.7.2. ............ 764
9.7.2.. ........................................................................ 764
9.7.2.. .............................................................................. 767
9.7.3. ,
....................................................................................................................... 774
9.7.3.. ................................................. 774
9.7.3.. , ........... 777
9.7.3.. ............................................................. 779
9.7.3.. ............................................................. 781
9.7.4. ......................................................................... 781

.
Z RZ,

681

682

Csp3Z, Nu:
, RNu - CNu, s- CZ
:

Nu: +

C-Z

Nu-C

+Z

Z (
). ,
.
, , (OTf), Z-=FSO-,
FSO3-, - (OTs-) .
, -
(RCO-), F-.


.
.
1.

Nu: + RZ Nu+-R + Z-.

:
H3N: + R Hal
R3N: + R Hal
R3P: + R Hal
R2S: + R Hal
ROTs + A cOH

R
R
R
R
R

NH3Hal

4 N Hal
4 P Hal ;
3 S Hal ;
OAc + T sOH

(Ts - - 3
ROH + HBr
R1OR2 + HI
RHal + ROH
RHal + HOH

RBr + H2O;
R1I + R2OH;
ROR + HHal;
ROH + HHal.

682

SO 2

683

2.

Nu:- + RZ NuR + Z::

RO + R1Hal
RS + R1Hal
CN + RHal
Hal + RHal'

ROR1 + Hal
RSR1 + Hal
R-CN + Hal
RHal + Hal'

;
;
;
.

( ,
RI + I*-

RI* + I-).
NO2

+ RHal

RNO2 + Hal

+ RONO

R
R1R2C

C R3

R1

+ RHal

N: K + RHal

NR + KHal

O
O

R3 + Hal

R2 O

O
-

RC

RC

+ R1Hal

N3

+ RHal

RC

C: + R1Hal

O
OR1

+ Hal

RN3 + Hal ;

RC

CR1 + Hal

3. -

Nu: + RZ+ Nu+-R + Z::

:S

XNH2

NH2

NH2

C S R + (CH3)2S
NH2
S-

+ RS(CH3)2X

683

684

4.

Nu:- + RZ+ NuR + Z:

:
O
R1COO

R1

+ R3O BF4

+ R2O + BF4
OR

CH3
C NO2 + (CH3)3N:

RCH2

(H3)3CHNO2 + RCH2N(CH3)3

CH3

RC

O
O

+ R1N(CH3)3

RC

O
OR1

+ (CH3)3N:

,


.

, SN2 (substitution nucleophilic
bimolecular) SN1 (substitution nucleophilic monomolecular).
3 (3.1) : 1)
, 2) , 3)
. SN2
, a SNl :
Nu: + R
RZ

Nu
R +Z

R + Z:
Nu

SN 2

RNu

SN 1

.

684

685

1930- ..
.. ,
,
.
.
SN2 SN1- ,

.

9.1. SN1 SN2

SN1

,
.

(), ,
. ,
. 9.1, .

685

686

H
+

Nu

Nu

H
C
R1 R2

R2

SN2

R1

H
Nu

C
R1

R2

. 9.1.

SN1 (a) SN2 (). SN2- ()

.
1. ,
:
= -

d [ RZ ]
= k 1 [ RZ ] .
dt

,
, Nu:.
2. ,
RZ ,
. ,
, ,
, .
, .13.
, R+, SN1-
RZ.
3. ,
Z-,
, ,
.
4. , ,
, ,
. ,
() SN1 - .

686

687

SN2
,

(. 9.1). SN2-
-
Z Nu (. . 9.1).

()
*- C-Z ().

.
1. ,
:
=

d [ RZ ]
= k 2 [ RZ ][ Nu] .
dt

,
, ,
SN2-pe
SN1.
2. SN2-

. SN2-
, -
(. 9.2.2) ,
. Nu:
RZ , Z, ,
CNu
CZ
(. 9.1,).

,

. 9.2.1.
SN2-.

687

688

, , ,
,
(+)-2- -
(, , 1935):
H
131

I +

131

+ I

CH3 C6H13

CH3
C6H13

(+)-2-

(-)-2-

() . ,

.
9.1

/3

CH3F

-142

-78

0,87 -78o

31

-97

-24

0,92

-96

1,73

3I

-66

42

2,28

212

-96

40

1,34

13

-63

61

1,50

14

-23

77

1,60

+8

150

2,89

CH3CH2,F

-143

-38

0,82 -38o

321

-140

12

0,92

32

-120

38

1,43

32I

-111

72

1,94

322F

-160

-3

0,78

3221

-123

47

0,89

322

-110

71

1,35

3,22I

-101

102

1,75

(CH3)2CHF

-133

-10

0,77

(3)21

-117

36

0,86

688

689

(3)2

-89

60

1,31

(3)2I

-91

89

1,70

CH3(CH2)3F

+32

0,78

3(2)31

-123

+78

0,89

3(2)3

-112

101

1,30

3(2)3I

-103

131

1,62

(3)31

-28

51,5

0,85

(3)3

-20

73

1,23

(3)3I

-12

100

1,54

CH3(CH2)4F

63

0,78

3(2)41

-99

108

0,88

3(2)4

-95

130

1,22

3(2)4I

-86

155

1,52

3(2)51

-94

135

0,88

3(2)5

-85

156

1,18

3(2)5I

180

1,44

1 -

3(2)71

-61

182

0,87

1-

3(2)7

-55

201

1,12

1 -

3(2)151

149/1

0,87

1 -

3(2)15

+17

190/11

0,99

2=21

-136

46

0,94

2=2

-119

71

2=2I

-99

102

1,85

9.2
SN2-
I 50

31

200

-611Cl

0,003

321

2,50

6521

100,000

3231

1,10

321

36,000

32221

1,00

1225

1700

-6131

1,30

C1CH2CN

3000

-12251

1,20

CH3CHCH2Br
CH3

689

0,040

690

CH3CHCH3

0,02

()32

2. 10-5

0,02

32

2,200

32C22

1,000

Cl

CH3CHCH2CH3
Cl

2=21

79

6521

200

3. SN2-
,
.
,
,
. SN2-

>

C2H5 >

R2 >

R2CH >

R.

SN2 .


.
. 9.1. . 9.2

50 ". ,
. 9.2, , SN2-
-
> 2 ~ 22 >> ()2, ..
.
R3 - SN2 . SN1-

, E1- (. 10).
690

691

,
,
SN2-, SN1- Z RZ Nu (
. 9.4.2). SN2- > R >> R2CHX

.
, , - .
KI
(2,2) > 22 (1,0) >> (CH3)2CHCH2Br (0,04) >
> ()2 (2,0 10-5).

.
-
Nu: - ,
-.
(-) ,
a, .
-
- .
SN1-
: R3 > R2CH >> RCH2.
- SN1-,

SN1, SN2-,
RCH2X SN2-.
, SN1- SN2-
, ,
.
,
,
,
, SN2-.
691

692

. ,
.

,
- , :
C6H5CHCH3 + CH3COOK

CH3COOH,
50oC

C6H5CHCH3

Cl

(15%
)

OCOCH3

C6H5CHCH3 + (C2H5)4NOAc

; 50oC

C6H5CHCH3

Cl

OCOCH3

C6H5CHCH3 + H2O

-; 50oC

Cl

C6H5CHCH3
OH

(65%
)

(33%
)

- .
, 100%- ,
.
-,
, , SN1- SN2.

.

9.2. SN2
9.2.1.

, SN2-,
, . , ,
, ,
.
SN2- .
(1895 .), .
,

692

693

() (. . 8). ,
(-)- () 15 (+)- ; ,
(-)- (-)- :
CH2COOH
CHOH
(-) COOH

CHCl
(-) COOH

CHCl

OH

SOCl2 AgOH

CH2COOH

CH2COOH

PCl5

COOH (+)
AgOH SOCl2

CH2COOH

OH

CHOH

PCl5

COOH (+)

, , -
, ? (. 8.3),
,
. ,
,
,
,
, .
, ,
; ,

.
, ,
, -. ,
:

693

694

R2

R1
OH

H (-)

TsCl

R2

R1

OTs
H (-)

R1
(-)

OAc

KOAc

AcO
(+)

Ac2O

Ac2O
HO

()

R2

KOAc

TsO
(+)

R1
R2

TsCl

R1
R2
H

HO
()

R1
R2

HO
(+) H

,
,
.
, (. 18, .
3) (. 11) .
,

.

. ,
OTs -, OR-, - .
,
- , .. .

,
2-, 1- 2 NaI LiBr
:

694

695

C6H13
+
I
H3

C6H13
*I

H
I

CH3

CH3
(I)

C6H13
H

I*

CH3

C6H13
H + I

*I

C6H13
I* + I

H3

(II)

,

.
, ,

, ,
.
, SN2- (I).
() SN2-
. ,

(I), ..
,
SN2- . ,

,
,
(II), ,
,
. .
9.1

695

696

C6H5

CH3 (-)

SCH3

H C6H5 CH3
S
Br
CH3 (-) CH3

CH3Br

H C6H5 CH3
Br
S
CH
3
CH3 (-)

(CH3)2S

Br

Br

C6H5
H
CH3 (+)

, :

.

9.2.2. SN2-

SN2-
. , I

, II,
I ,
II. ,
9.1, ,
,
, .
SN2
. (.
9.2, ) , CZ,
, ,
( )
CZ. ,
* . ,
, C

696

697

. (. 9.2, ),

; , , *
,
(. .2, .1). n-,
*, , . ,
, , .
9.2, . , (. 9.1, )
(. 9.1, a).
=

C-Z

Nu

C-Z

Nu

*
*

Z
Nu

Nu
Nu

Nu

Z
C

Z
Nu

. 9.2. SN2-
() () (Nu) CZ.

- ,
Nu
( 20 /),
SN2- . SN2
CZ
CNu,
(. 25, . 3), ,
.
697

698

SN2-
. ,

, - - -4.
Cl

H
Br
+ Cl

+ Br
HO

HO
H

H
H

Br
H
+ Cl
HO

Cl
+ Br
HO

9.2.3. ,
SN2-

Z RZ SN2- ,
, .
Nu:,
Z:,
Nu: 3Z .
, ,
()
.
.
SN2 ,

698

699

9.2.3.. SN2-

,
.
Nu: + CH3Z

NuCH3 + Z:

(9.1)

. 9.3.
Nu-...CH3Z, Nu3...Z-.
, (Nu- +
3Z),
(CH3Nu + Z-). ,
(.3, . 1). ,
, ,
3Z NuCH3
.
,
[Nu ... ... Z]-
( Nu:- Z) . -
. , Hal...l, 8,6 14,4
/.
-....,
() (-) (. 3, . I).

699

700
. 9.3. SN2-. 0 -
; H - ; H -

:
k1
k -1

Nu: + CH3Z

k2

[Nu ...CH3Z]

[Nu ...CH3Z]

(. 3),

k=

k1k 2
.
k 1 + k 2

, k
, . k1>>k2,

k1
k , ..
k 1 2

[Nu-....3Z]. SN2-
, k-1>>k2,
, .

Nu-, Z,
Nu- Z
.
O

CH3Nu + CF3COO

Nu:

+ CF3C

Nu:

+ CH3OC6H5

Nu:

+ CH3Br

CH3Nu + Br

Nu:

+ CH3Cl

CH3Nu + Cl

Nu:

+ CH3F

CH3Nu + F

OCH3

CH3Nu + C6H5O

700

701

,
Nu:- .
:

- > F- > 3- > 3S- > CN- ~ l- > r-.

,
Nu-H (. . 3.8 . 3) (
, F- 3- ).

, SN2-
, ..
.
9.2.3..

SN2- 1020 , :
F

+ CH3Cl

25

FCH3 + Cl

; k =1012/.;

+ CH3Cl

2
25

FCH3 + Cl

; k =10-8/.;

, . ,
F- > N- > r- > I-
, (N- > r- >
I-) , .

SN2-.
,
. 9.1, 9.4. ( 2). ,
.

701

702

,


.
,
(9.1)
,

Nu Z . ,

. 9.4.

, . 9.4.

(1)
(2)

,

,
. , SN2 - :
Nu . nS + CH3Z . mS

[Nu ...CH3Z] . (m+n-2)S + 2S

(S ).

(H . 9.4)
- .
,
. , ,
, , .
[Nu ...CH3Z] . (m+n-2)S + 2S

702

703

, SN2-

.
(. 9.4).
.
, SN2
.

9.2.3..

(. 9.4, 2) , ..
.

G,

(. 3, . 1).
G, .

.

, (. 9.5).
I G ,
, .
II ,
. G , ,
. (
III), G ,
. ,
, ,
.
, ,
.

703

704

. 9.5. :

(I) (II) ;
(I) (III)
. GI; GII GIII
I, II, III; ; ;

. .


.
, ,

,
.
, ,

704

705

, ,
. ,

.

,
. , ,
,
,
.
, ,

. . 9.3

. SN2-,
SN1-, 9.3.
9.3

) SN1

RZ

R+...Z-

) SN1

[RZ]+

R +..Z +

) SN2

Nu+ RZ

Nu +...R... Z -

) SN2

Nu-+ RZ

Nu -...R...Z -

) SN2

Nu + [RZ]+ Nu +...R...Z -

705

706

) SN2

Nu_+ [RZ]+ Nu...R...ZS+

-,
- (. 9.3),
335 000 , .
() . 9.2.
()

:

C2H5SBr

C2H5 + +
S C2H5
C2H5

70oC

=
Br

H3OH

6H5NO2

HCl3

180

230

290

, 70

(C2H5)2S + C2H5Br

()
(
), -:
N + BrCH2C

N CH2C

C6H5

Br

H2Cl2

6H5CN

14

16

22

25

, 30

C6H5

, ( (),
-)

:
*I + CH3I

, 0

0oC

CH3*I + I

H3OH

2H5O

H3

27000

65

22

706

707

SN2- ()
:
(CH3)3N: + (CH3)3SNO3

, 40

40oC

(CH3)4NNO3 + (CH3)2S

H3NO2

2H5O

H3

119

10

:
HO + (CH3)2S

100oC

CH3OH + (CH3)2S

% 2
25 - 2

, 100

20

40

100

20000

480

40

,

.

-

, - - . ,

G, H,

S, .

.

.
SN2- -

707

708

SN2-
Nu:- RZ ,
.
,
.

Nu- . G
, ,
. , ,
.
(, , , ,
.)
. , ,
(. 3).

,
F-; O-; R-; RCOO-; CN-; NH2-; NR2-.
, , ,
, .
-
,
.
,
. G
Nu-: (. 9.5,).

2 > 3 > C2H5 > NH2 > 3NO2 > CH3CN > > >
~ N-.

.
.
KCN
, :
708

709

RCH2X + KCN

100oC

RCH2CN + KX

- (.21, .3)
, . - RCOO ,
,
.
N-
:

O
C O Na + R'CH2X

O
RC OCH2R' + NaX

, (KF, LiF, KCN; NaCN,

RCOONa .),
, (); ; , .
, ,
, (C4H9)4NCN, (C4H9)4NN3 .,
-3; -2; -2, 5-10%
.
Nu-
,
SN2- Nu- RZ.
, ,
,

(. 3).
G.

- SN2-
. . 9.4
SN2- :
l

+ CH3I

k2
25oC

CH3Cl + I

709

(9.2)

710

N3

+ -C4H9Br

k2
25oC

-C4H9N3 + Br

(9.3)

, . 9.4, SN2- 103-106

,
, N--2
.
SNAr (. . 15). , . ,
n- - 105 1017
, .

, .. .
- SN2-
,
, F-; RO-; -; 5O-; RCOO-; l- .. (. 9.5).
9.4
SN2- (9.2) (9.3)
25o

K2

(9.2)

(9.3)

, 3

N-, CH3CONHCH3

8,5

, HCONH2

12,5

11

N-, CH3NHCHO

45,3

()

400

, CH3CN

45000

5000

, CH3COCH3

1,6.105

4000

, CH3SOCH3

1260

SO2

, (CH3)2NCHO

8 10

N,N-, CH3CON(CH3)2

2,5.106

710

2500
7950

711
()
N--2
N

7,4.106

2.105

O
CH3

()
O=P[N(CH3)2]3

9.5

lg

k 2 ( )
k 2 ( )

Cl-

5,9

r-

4,8

I-

2,6

N3-

5,1

C6H5O-

6,3

C6H5COOCH3COO

5,45
6,2

, , I-;
CNS-; RS- , SN2-
, ,
, ..


. ,

(. 9.6).
- SN2-, ,
I- > r > l- > F-.
, ,
l- > r- > I-,
(. 9.2.3.).
,
711

712

(.. )
.
-
,
,
, , : F- > l- >
r- > I-.
,

, .
,
, ,
, (. 9.2.3.6).
9.6
SN2-

CH3I + M+X-

; 25o

C6H5S->S2O32->I->SCN->CN>3O->Cl->CH3COO->F-

CH3OTs + M+X-

3; 25o

C6H5S->CH3O->I->SCN>Br->Cl-

CH3OTs + M+X-

; 0o

Cl->Br->I- (9:3:1)

-C4H9OTs + N+(C4H9)4X-

; 25o

Cl->Br->I- (18:5:1)

-C3H7OTs + N+(C4H9)4X-

; 25o

S2O32->OH-~CH3O->F>Cl->Br->I-

C6H5CH2OTs + K+X-

; 30o

CH3OTs + (C5H11)4N+X-

N3->CH3COO->CN->F->Cl->Br->ICl->Br->I- (18:5:1)

N+(C5H11)4X-; 180o;
CH3Br + X-

OH->F->CH3O->CH3S->CN->Cl>Br-

712

713

9.2.3..

.

(),
(l3; CH2Cl2; 6H53; C6H6 .),
.
. , . .
.

RZ
Nu-.
.
M+Nu-. RZ,
Nu-. +Nu-, M=Li, Na, K,
Cs .., ,
, , , .,
,
RZ Nu- .
R4N+Cl-,
R4N+Br- R4P+Cl-,
, .
, .

+Nu-:
(1)

+ -

Q X (.) + M Nu (.)

+ -

Q Nu (.) + (.)

Q+= R4N+ R4+ .

Q+Nu-, Nu_,
. Q+ (R4N+; R4P+)
:

713

714

(2)

Q Nu (.)

Q Nu (.)

:
(3)

+ -

Q X (.) + RZ

SN2

+ -

RNu + Q Z (.)

Q+X-
:
(4)

+ -

+ -

+ -

Q Z (.) + M X

+ -

Q X (.) + M Z

, . , :
+

Q Nu + RZ

RNu + Q Nu (.)

+ -

+ M+ Nu + Q Z (.)

Q Nu + M Z

Q+ , Nu-= CN-; SCN-; NO2-;

RCOO-; N3-; RS- .. Q+Z-,
, ,
.
Q+ Z- -
Nu-.

, ,
.
R4N+ R4P+ , 4
1016 , , . C6H5CH2N+(C2H5)3Cl-;
(C8H17)4N+Br-; (C4H9)4N+C1-; C16H33N+(3)3-
.
(CH2Cl2, l, 6, 5
.) R4N+Nu-,

714

715

. Nu-
, -, ,
, -,
( 45 ) R4N+
Nu- , ..
.
SN2-

NaCN -,
- (
).
SN2-,
:
+

6H5CH2N (C2H5)3Cl

H3(CH2)7Cl + NaCN -; 100o CH3(CH2)7CN + NaCl

(95-100%)

C6H13Br + NaN3

H2O-C6H5CH3; 100oC
+

2RHal + Na2S

(C8H17)3N CH3Cl

(92%)

N (C4H9)4Cl
H2O-C6H6; 70oC

RSR + 2NaCl
(85-97%)
+

Cl(CH2)4Cl + N aOH

C6H13N3 + NaBr

(C8H17)3N CH3Cl

+ 2N aCl

H2O-C6H6; 80o C

O
+

CH3(CH2)7OH + -C4H9Cl + NaOH

(88%)
-

(C4H9)4N HSO4
H2O-C6H6; 50oC

CH3(CH2)7OC4H9- + NaCl
(80%)

, .
.


.
, - ( . crown

715

716

- ), .. (. 11).
18--6, 15--5 [2,2,2]- (
- , -
):
O

O
O

18--6

O
O

O
O

O
O

15--5

O
[2,2,2]-

,
.
,
,
, , - (; N; S; ),
. ,
- ,
. + 18 . 15--5, 12--4.

,

,
. Nu-
,

. ,
,
, ,
. ,

716

717

, .

. ,
, , -
.

: F-, l-, RCOO-
, , N3-. .
:
CH3COOK + -C6H13Br

(CH3)3COOK + BrCH2C

18--6
CH3CN; 28oC

O
C6H5

C6H6; 80oC

(95%)

-C8H17OSO2CH3 + KF

C6H5CH2Cl + -C4H9ONa

+ KBr
H
OC
6 13-
(100%)
.

18--6

O
O
(CH3)3CC OCH2 C C6H5
C8H17OSO2CH3 + KCl

CH3C

+ KBr

18--6
100oC
18--6
CH3CN; 80oC
18--6
; 65oC

C8H17Cl + CH3SO3K

-C8H17F + CH3SO3K
(92%)

C6H5CH2OC4H9- + NaCl
(87%)

:
(. 5, . 1), ..

9.2.4.

, SN2-

717

718

, - CZ
.
,
. , , ,

. ,

SN2- :
Nu:

[Nu (R-Z)-

+ R-Z

, ,
-.
,
. - (RZ)-.
Z- R..
R. Nu. RNu:
[ Nu (RZ)- ] [Nu , R, Z-] RNu + Z -.
SN2- SET (single electron transfer).
, ,
(. 15),
,
(. 20, . 3) . SET-
, ( ; . . 14)
(, -
, )
. , ,
,
. :
, SET-,
, ?
. c (1985)
.

718

719

-,
. ,

. ,
.

SN2-
:
Nu:

+R

Nu

R + Z:

NuR ,
SN2. R

RZ. Nu- RZ R
Z; Nu. R.
.

(. 3). ,
Nu. (RZ)-.
, (RZ)-. R. + Z- Nu. R.
. SET- ,
. .
, ( ) SET,
Na+ , R..
Na

+R

SET

Na + R + Z:

, SN2,
( )

719

720

.

, .

,
. . 26 (. 3)

.

9.3. SN1

SN1 : 1)
CZ RZ
R+ Z- 2)
R+ Nu Nu-, :
RZ

k 1
k -1

R Z

k 2
Nu

RNu

(9.4)

, SN2-,
. C-Z
, .
. 9.3,
( 3 ),
:
=

k 1 k 2 [ RZ ][ Nu}
k 1 [ Z ] + k 2 [ Nu]

(9.4)

2[Nu]>>k-1[Z-],
SN1-

720

721

= 1[RZ]

(9.5)

. 9.5
.
- RZ R+ Nu
,
.
, SN1-.
,
R+
, , . ,
SN1-
,
.

. 9.6.

RZ ,
( 2)
RZ R+.
, ,
, .
,
( 2).
721

722

: > > . SN1-
,
. , -
SN1 (20 =58) 1 000 000 , -.
RZ
SN1-.
.

r3+, r2C+, rC2+
.
r3; r2,
. (5)3l
80%- ,
(C6H5)2CHCl,
, 1--1- 65(1)3,
.
(9.5)
SN1- Z. Z- ,
(9.6): v
= k1[RZ]. , ,
Nu.

(IV) SO2
(, , 1940). Z-=Cl- , ,
(9.5), . , LiCl, l-,
. (C6H5)2CHC1
SO2,

722

723

,
. SN1 ,
C-Z RZ,
(9.4).
() ,
, - SN1

SN2 - .
-
, .
, , -
10 30%, ,
, (

SN2-) ( SN1).
. (65)2 LiCI
(65)21 LiBr .
:
,
SN1-. ,
(LiBr (H5)2r LiCI
(65)2l), .
, , ,
, , ,
. .
.
SN1
, R+ Z-. ,
, ,
, . ,
, ,
SN1 -

723

724

.
SN1-.
,
Z-, ,
, .
.
, , N3- R+:
SolOH

RZ

ROSol + H

+ Z

+ Z
N3

RN3 + Z

SolOH .
- ,
RN3 ROSol,
( ) FN=

[ RN ]
3

[ ROSol]

. SN1 .
FN
Z- RZ.
SN1
1 .

( ),
( ).
SN1 ,

.
80%-
FN=

[ RN ] =1,94
3

[ ROH ]

,
(65)2r 34 ,
(65)2Cl ( 1-

724

725

). , , .
. ,
, SN1-
- - - - -
- .

FN
(65)31; (65)3Br; (5)3F -.
FN SN1: 3----1 (,-) 1--3-2 (,-). 3--3-1 .


. ,
,- ,-

,
.
NaBH4,
, ,
, ,-:
(CH3)2C CH CH2
Cl

,-

NaBH4; HOH
CH3CH2OH-H2O

(CH3)2C CH CH2

OH

(CH3)2C CH CH2Cl
,-

+ (CH3)2C=CHCH2OH + (CH3)2CH-CH=CH2 + (CH3)2C=CHCH3

,
, , ,
,
l-. , ,-
,-.

725

726

, .. ( )
.
-
. , ,-
R+Cl- .

SN1 -
, .

9.3.1.

, ,
,
.

.
. 9.7.
9.7

1. -C3H7C*HDOBs
-C6H13C*H OTs

2.

3; 99

100

3; 75

96

3; 64

77

46

CH3
CH3
-C6H13C* Ohph

3.

% %

CH2CH3

726

727

4. C6H5C*HDOTs
C6H5C* Cl
5.

90

20

3; 50

56

22

CH3
n-CH3OC6H4CH Ohph

3; 30

100

C6H5

6.

CH3
C6H5

7.

3; 25

3; 70

98

C C2H5

n-O2NC6H4C O
O

. Bs= O2SC6H4Br-n; Ts = O2S-C6H4CH3-n;

hph = OC
HOOC

(. 2)
,
SN1-
.
, , , , Z-
- R+,
,
.
n- -
100%- (1- . 9.7), ..
SN2-. 25
.
?
, SN2 SN1.
SN1-
, SN2 .

727

728

. ,
1- ( 5) , .. .
. ,
SN2. ,
. ,
,
.
,
,
, , ,
. , ,
.
,
,
. , ,
RZ ,
. 9.6 R+.
. ,
,
.
RZ ( )
R+Z-,
.
() R+Z-,
. -
. ,
- ,
- .

728

729

,
, .
,

.
R-Z
,
,
.
().
- -, . (5)3l , .
,
, (C6H5)3C+Cl-
(C6H5)3C+ . (C6H5)3CCl
- :
O
(C6H5)3CCl ... H-O-C-CH3

O
(C6H5)3C Cl ... H-O-C-CH3

,
.
RZ ,
SnCl4; SbCl5; ll3
(65)3l
:
(C6H5)3CCl

SbCl5; k

(C6H5)3 SbCl6

C6H5NO2

(C6H5)3C

+ SbCl6

(C6H5)3C+Cl- SO2 10 ,
, ,
, SO2. (IV)

729

730

-10o
:
(C6H5)3CCl

k ~10-2

(C6H5)3 SbCl6

k ~ 10-3

(C6H5)3C

+ SbCl6

. , -

.

(+)--3--2-. ,

,
.. ,
:
OCH3

H3CO

H
H3C

CH3
H

OBs

H3C

CH3

( 3
: )
,
OBs-, , .. .

.
,
,
- . , ,
,
OBs-.
- ,
:

730

731

RZ

k 1
k -1

R Z

AcOH

ROAc + HZ

(9.7

. k-1,
, -
,
. , -
, OBs-
.

LiClO4 ( )

, .

LiClO4

.
LiClO4
. 9.7. LiClO4 -

LiClO4

(+)--3--2--

(. 9.7). -

. b ,

[LiClO4]

,
. ,
.
- OBs-
lO4-.
,

731

732

. -
RlO3. ,
RO-ClO3 ,
ROBs. , OBs- ClO4-

k-1 R+Bs- ( (9.6)).
OBs- ClO4- ,
, - ,

, (. 9.7).
,
,
,
.

- ,
,
() -
.
, .
,

:
RZ

k1
k -1

R Z

k2

R Z

k -2

SolOH

ROSol

k3
k -3

+ Z

SolOH

ROSol

(9.8)
, R+Z-
. -
- - :

732

733

OBs + LiClO4

k4
k -4

ClO4 + LiOB

- R+OBs , -
R+ClO4-,
k-2 LiClO4. , -
, ,
R+ClO4-. LiClO4

LiOBs OBs- ClO4- - R+OBs-. , LiOBs
, .. ROBs,

.
,
- , , ,
, .
RZ :
k-3, k-2
k-1.

,- ,-
, -,
, -
. ,
NaBH4 ,
,
. , -
,

733

734

,
, , - ,
.


, , 3--2-, - .., , -3--2-,

, , -
.

--,
18, 90%- .
,
: 1)
, 2) 3)
()
.
1.
O
R*

NO2

(R)- (S)-

O
R O

NO2

(R,S)-

2.
O
R*

NO2 -, R*OH + HOOC

(9:1)

3. () 18

734

NO2

735
18

R*

NO2

R*

18

O
C

NO2

, .. k, k k
. k
k, , k> k. k> k
, 18 ,
.
,

, -
.
, 18O
-. , n-NO2C6H4COO-
. , , () .
, NaN3
n--n-,
18. N3 - ,
k-2 - .
, k-2 - ,
.
, k ,
,
.
18
n--n-, n-n-, -4--,

735

736

,
:
(C6H5)2CH-S
CH3CN

C N

(C6H5)2CH S

C N

(C6H5)2CH-N C S

, 3---2 , -,
, --- . ,
.
,
, OBs-
(. ).
C-,
180 ,
-, . -- , ,
- , 13
, .

9.3.2.

-, ,

( 9.2). ,
1, 2 3, SN1 (), SN1
() SN1() . 4,
5, 6 7, SN2 ( SN2 () SN2().
. ,
SN1 () k5 > k2,

736

737

, k2 > k5,
, ,
, 6 7.
9.2
-
RZ

k4 Nu

k1
k-1

R Z
()

k2
k-2

R Z
()
k6 Nu

k5 Nu

k3
k-3

R + Z
()

k7 Nu

. , -
; .

SN2- k4,
SN1- , ,
7.
SN2- (9.2.1), ,

, SN1-
: . , ,
, ,
---
NaN3 (.). ,
, .
-
.

9.4.

9.2
. -

737

738

,
SN2- SN1 -. ,
: , - SN1-,
SN2- SN1-
?
,
.

9.4.1.

,
SN2. 1973 . ,
3Z - SN2
()
,
.
, ,
SN1-.

. ,
,
.
SN2 SN1 (),
.
, .
SN2 SN1 () (.
9.2) , .
,
.
(. 9.7.2)
,

738

739

109 - 1012 ,
. ,
2-- 2--2: ,
108
. . ,
2- SN1 ()-, ..
,
2- ,
,
:
H
Br

H
Br ....HOSol

SolOH

, -
SN2- 2- (,
),

.

2--,
. ,

, 2- .

SN2
,
.
9.3, ,

(

739

740

)
. -,
, 2 .
HS + R-Z

[HS...R...Z]

S N2

HS + R-Z

[HS ... R Z ]

HS-R

R-Z

[R

SN1 ()
(. 9.2)

Z ]

(HS )

9.4.2.

ArCH2Z
.
, ArCH(Alk)Z
- ,
SN2
. ,
: : SN2
SNl ()?

,
. ,
( ),
SN2- ,

:
Nu

+
-

SN2

740

741

, (+)-,
(-M)-.
,
. ,

. . 9.8. , (n-3; n-3; n-OR; NHAc; SR
..) (
),
(. . 3).
, ,
:
ArCH2OTs + 3 23 + TsOH
( = -5,7 , -2,3 )
ArCH2Cl + ArNH2

ArCH2NHAr + HCl
(

XC6H4CH2Z

;
ArNH2 , ()

: =-0,59 n36H42l, = -1,55 nN242l.
,
. 9.8.

(. 9.8), ,

ArCH2Z

. ,
, .

1.
SN2 SN1,
SN2- SN1 - , ..
.

741

742

2.
, .
,
()
, , ,
():
+

Nu: ...............CH2..................Z

Nu: / / / / / / CH2 / / / / / / Z

Ar
(A)

Ar
()

,
,
,
.
,
, . 9.7,
-- -
70%- 20 .
, , SN1 (),
k1(PhO)/k1(MeO)=135. ,
. 9.7 (
), k1(PhO)/k1(MeO) . ,
, N3-,
-l,

. NO3-, PhSO3-)

,
, SN1-.
9.7
n-PhOC6H4CH2Cl n-OC6H4CH2Cl 70%-
20

k2(PhO)/k2(CH3O)

k2(PhO)/k2(CH3O)

NO3-

139

Cl-

87

742

743
PhSO3F

125

Br-

15,5

86

N3-

4,9

,
, ,
(. 9.4.3)
SN2 SN1 .
SN2-,
,
,
, ,
.

SN1 () SN1 ().
,
, , SN1 () SN1 () SN2
SN1 (). , -
SN2 SN1-,
.

9.4.3.

SN2-, SN1- Z
,
Z-
. ,
HZ ,
, Z-= 6H4SO3-.

pKa (HZ),
:
Z=

RSO3 ~ ROSO3 > I > Br > Cl > Me2S+ > NO3 > F > RCO2 > Me3N+

743

744

pKa (HZ)

~ -5

~ -2

-10 -9

-7

-5

-1,3 3,2

10

, ,
, ,
.


1- 1- 80%-
75 o:
PhCHCH3 + HOH
X

75 oC
HOH-C2H5OH

PhCH-CH3 + HX
OH

X- =

CF3SO3-

n-O2N-C6H4SO3-

TsO-

CH3SO3-

I-

Br-

1,4.108

4,4.105

3,7.104

3.104

90

14

CF3COO-

Cl-

F-

n-O2N-C6H4COO-

CH3COO-

2,1

1,0

9.10-6

5,5.10-6

1,4.10-6

( )
: F3- >> 3- nN26H4SO3- > n-CH36H4SO3-. -
I- > r- > l-,
F > l > r > I.
RSO3-,
- -
(kCF3SO3-/kCl- ~ 108). ( !)

0-5 o.
, -,
() F3SO3-,
n-3H4S3- ().
, , 100 000
.
SN1-, SN2-
, .

744

745

SN1- C-Z ,
SN 2,
,
.

. ,
, H2SO4.
F-, a HF:
RF + H

R-FH

Nu

RNu + HF

:
I

Me-O-R

MeI + ROH

H
- ,

r-, l-, NO2-, H2O, EtOH, PhOH, ,

, SN1-.

(2, EtOH, PhOH) ,
, ,

. , SN1, ,
ROH -
:
t-Bu-Br + HOR

t-BuBr ... H-OR

[t-Bu ... Br ...H-OR]

t-BuOR + HBr

,
.
,
I < Br < 1 <
F, . , 3 -
25 o = 1, Br, I

745

746

1:250:2000, 1:60:100.
SN2
9.2.3., .
SN- ,
, (. II):
ROH + HCl
RBr + H2O

Ag

ZnCl2

RCl + H2O

ROH + AgBr + H

9.5.
9.5.1.

,
, .. ,
. , ..
, .

, ..

,
(sp3- RZ, sp2-
R-C(O)-Z ..).
,
.
,
sp3-
sp2-
, RS+ Z-
(II) ..
, ,

746

747

. ,
,
(. 3).

SN2- SN1. SN2-

. SN1-
,
, R+

.
SN2- ,
. : 1) ,
2) , 3) , 4)
, 5) 2- , 6)
. ,

. , ,
, I- > r> l- > F-; RSe- > RS- > RO-; R3As ~ R3 > R3N,
.

, . SN2-

C-Z (9.2.2),
SN2.
,
(. 9.2.3.).

G SN2-.
, Nu: R-Z

747

748

,
SN2- ( ).
,
- ,
SN2-.


.
(), (1953)
( nCH3I )
, . . n =0,00. ,
k Nu
3 25 .
nCH3I = log
k CH3OH

.9.9 nCH3I
. ,

- . -,
- -
3I ,
. I- HOO- , Ka
20 . , -
- , nCH3I -
, -. ,
, ,
.
nCH3I , 3- > 65- > > NO3-.
: - > F- RS- > l-, . , ,
: RSe- > RS> RO-; R3Sn- > R3Ge- > R3Si-; I- > Br- > l- > F- ( ).

748

749

, , ,
.
9.9
3I

nCH3I

Ka

nCH3I

Ka

0,0

-1,7

NH2OH

6,6

5,8

NO3-

1,5

-1,6

NH2NH2

6,6

7,9

2,7

3,45

(CH3CH2)3N

6,7

10,75

6,7

9,3

7,1

7,4

-10

7,8

11,6

8,7

8,7

9,9

6,6

F3
l(CH3)2S
NH3
N3C6H5O
r

4,3

4,74

4,4

-6

5,3

CN

(CH3CH3)3As
I

5,5

9,24

HOO

5,8

4,72

(CH3CH2)3P

5,8

9,9

5,8

-8

3O-

6,3

15,7

6,5

15,7

C6H5S

C6H5Se

10,7

(C6H5)3Sn-

11,5

(. 9.2.4). . 9.9 ,
, - .
( .)
- F- > l- > r- > I-,

(9.2.4). SN2-
,
, . 9.9. ,
,

749

750

,
.

SN2- (. 3).
, sp3-
. SN2-
,
(RS-; RSe-; R3; OO-; RC=- .) (F-; RCOO-; RNH2; -; RO-; NO3-; ClO4- .).
, ,
,
, .
.
SN2- ,

9.5.2. -

,
, ,
, ,
. , ,
NH2-NH2 N2OH
, , - HOO ClO- (. 9.9). . -

750

751

HO

HO

HO

(. 2),
, ()
.
, , SN2.
,
.

9.6. SN-

9.6.1. SNi

,
,
. ,
.
, ,
,
SN i (internal nucleophilic
substitution):

751

752

C6H13

C6H13
H
CH3

H
O

H
-CO2

CH3

C6H13

Cl

Cl

Cl

CH3

,
:

ROH + SOCl2

RO

O
S Cl + HCl

RCl SO2,
.
,
.
. ,
, :
2H5

H
CH3

2H5
O

H
CH3

Cl

Cl ()

C2H5 ()
Cl
H
CH3

,
- SN1-, S-Cl
.
. ,
, . .
, . ()

752

753

, SO2 l-
:
2H5
H
CH3

OSOCl

2H5
H
CH3

O-SO
Cl

Cl

2H5
Cl H
CH3

CH3

Cl

CH3

C2H5
H

C2H5

2H5
H
CH3

OSO

Cl

.
,
:
3H7
H
D

OSOCl

3H7
H
D

OSO
Cl

3H7
H
Cl D

OSO

Cl

C3H75
H + SO2
D

, SN i- SN1-,
.

9.6.2. (SN)

,
; (. 9.4.2).

SN. :

753

754

-Z

Nu

Nu

Nu
SN1 SN2 ( SN2').
. 9.10 1--2 -1 .
9.10

(A) Nu + CH3CH=CH-CH2Cl

CH3CH=CH-CH2Nu (Y)

(B) Nu + CH3CHCl-CH=CH2

CH3CHNu-C=CH2 (Z)

, %

2 EtO-/EtOH, 100

100

100

0,8 OH-/H2O, 25

60

40

38

62

EtOH, 100

92

82

18

, , SN2
, .

SN2' (. ). ,
MeCH=CHCHZMe (Z = -)
90%- , 2=2l ClCH2CH=CMe2
. ,
.
, SN2 ().

754

755

k1

k-1

()

()

Nu

k5
Nu

k'5

Nu

Nu

,
SN2:
Nu:

CH2=CH-CH2-Z

Nu-CH2-CH=CH2 + Z

-, :
d c

Z
c
b

Nu
Z

c
b

b
a
Nu

(-SN2')

d c
Nu

Nu

(-SN2')

a b

-, .

,

:

755

756

Nu

. -SN2- SN2 :
Z

Z
Nu

Nu

Nu

, -
- SN2 (), ,
,
.

9.6.3.

( ;
) S(CH2CH2Cl)2
, .
2- 32-
. Et2NCH2CHEtCl
Et2NCHEtCH2OH.
:

ClCH2CH2

S CH2 Cl
CH2

ClCH2CH2

ClCH2CH2SCH2CH2OH

756

CH2
CH2

H2O

757

Me
H

Br

CH2

HO

HO H

Et2N

Me
H O

Me

Et2N

CHEt Cl

CH2

Et2N CHEt

CHEt

CH2OH
OH

,

- ( )
.
9.4.
9.4

Nu

X:

X:

C Nu

X:

kC

Nu

kS

Nu

1. .
(
).
.

C-Z (k 9.4), ,
kC kS,

757

758

(kS) .

. , ,
,
.

2. . ,
, .
, SN2 SN1
,
(. ).

3. .
,
.
,
.
-, - .

,
. (1939). ,
-3--2- r 2,3, - .
Br
H
CH3

Br

OH
H

CH3

Br

CH3

OH
-

CH3

CH3
H

CH3
H
Br

HBr
-H2O

H
CH3
CH3

H
CH3

Br

758

CH3
H
-

Br

759

Br

H
CH3

H
H3

HO

H
CH3

H3

Br

CH3

HBr
-H2O

d,l

CH3
H

CH3
H

Br

CH3

OH
-

Br

H
CH3

Br

Br

H
Br

CH3
H

CH3

CH3
H
Br

.

.

.
N--3-

Et

Cl

Et

Cl

Nu

Et

Nu

N
H

14 .
104
( ).

.
.
-2-

759

760

18

CH3

CH3

OTs

OCOCH3

OAc

H
O18

Cl

18

H
H

OAc

OAc

H
H

OAc

18

OCOCH3

CH3

18O

.
.
-4:
CH3

T
H

OTs

CH3O

CH3
OTs

H
H

T
AcOH

OAc

CH3O

OAc

CH3O
T

-, 1 4,
.

.
,
-. ,

760

761

,
- .
- .

-3--2- (. 9.3.1).
- ,

. -
- .

-
C-OBs:

CH3O

H
Me

H
Me
H
Me

OBs

H
Me

Ar

Me
H

Me

Ar
H
Me

()

CH3O

H
Me

OAc

AcO

OBs

Me

H
Me
Me

OCH3

H
Me

Ar

OCH3

H
Me

Me

Me
H
OAc

AcO

Ar
Me
H

()

- ,
,
,
. :
Ar

H
OBs

H
Me

Me

, -- 7%
- 93% -. -
761

762

.
, -,
SN2. , - .

:
EtOH
14

14

CH2 CH2

CH2 CH2 OEt

OTs

CF3COOH

14

CH2 CH2OCOCF3

14

CH2
CH2
OTs

14

CF3COOCH2 CH2

SN2-, ,
,
- SN1 ,
14.
-
. ,
.
-7-:
H

OTs

OAc

AcOH

1011 , ,
.
- -.
- - :
- ?
, -
,

762

763

. , ,
(. . 26, . 3).
R

+ Nu

+
Nu

Nu

-
, ,
-, ,
..
. 26.

9.7.

9.7.1.

,
. SN1-

R3C+. ,
1902 . . . ,
R3C+, ,
, ,
, NH3 - , NH4+ - , 3 - , PH4+ -
. R3C+ , , ,
R3C .

.
763

764

.

CH5+, CR5+ .. S (. 4.10), .
,

, ,

:
:2 + + 3+,

4 + + CH5+

() -

:

.
,
,
.
sp2- .
sp2-
,
2p- ,
.
.

9.7.2.

9.7.2..

764

765

RX
R+ - ,
.
3l
:
(1)

3Cl +Cl

= +84 /

(2)

3 3+ + -

= +226 /

(3)

Cl + - 1-

=-83 /

3Cl 3+ + Cl-

= +227 /

(1) (3)
-l 3l
. - - (2)
- R.,
RX . . 9.11
RCl .
9.11
RC1
RC1 R+ + l-

H, /

H, /

3l

227

CH2=CHCH2Cl

187

32l

191

C6H5CH2Cl

180

CH3CH2CH2Cl

187

C6H5Cl

223

CH3 CH CH3
Cl

172

(C3)3-Cl

157

-
, r RBr R+ r-

765

766

( 2 /). , . 9.12,
.
9.12
RBr R+ r-

D(R+Br-), /

218

33+

182

3+3

163

D(R+Br-), /

(3)3+

149
161

3+=O

151

.
RX X- . + e- = -, R+
RX - e- R+ + .
= I(R.) + D(RX),
R+, I(R.) R. - - R+, D (RX)
RX R. ..
I(R.) ;
I(R.) R.,
R+. . 9.13
.
9.13
.

I(R ) R* (R - e = R )
R+

I(R.),

H R+,

227

262

32

192

322
(3)2

I(R.),

H R+,

(3)3

157

174

221

2=

218

187

209

2=-2

188

226

173

192

C6H5CH2

179

215

,
- (. 9.14):

766

767

R+ + H- RH + H /,
H R+ - -.
9.14
-

R+

R+

-H , /

- H , /

3+

314

2=-+-

237

22+

274

2=- +(3)2

225

(3)2

247

3 = --3

225

230

2=+

287

52+

233

5+

298

C6H5-CH -CH3

226

65C+(2)3

220

2=-CH2+

256

(3)3+

223

200

, . 9.11-9.14, ,

> > > .
SN1 - .

,
-.
;
, -
-49+ < -511+ < -613+,

32+ < 322+ < 3222+ <

3222-2+.

.

9.7.2..

767

768

,
, H
R+, Z- .
,
, Z-. .
,
, ,
.
-
,
(SOzClF - SbF5; FSO3H - SbF5; FSO3H - SO2 - SbF5),
.. ,
, .
3 4.
FSO3H Ho -15,
FS3 SbF5 H= -18.
SO2FCl SbF5 FSO3H - SbF5 - SO2 (.),
0 -120 o.
SO2FCl - SbF5
,
FSO3 - SbF5 - SO2(.):
SbF

5
RCl SO FCl
R SbF5Cl
2

ROH

FSO3H - SbF5
SO2 (.)

ROH2

+ H3O

- ,
:
(CH3)3CH

FSO3H - SbF5

(CH3)3C SbF5FSO3

768

+ H2

769

, ,
- .
110 o FS3 - SbF5 - SO2FCl FS3 - SbF5 - SO2
:
ROH + H

FSO3H - SbF5
SO2FCl, -110 oC

ROH2

32+ CH3CH2OH2+ +50 o,

3+ 32+,
.
RCH2+
. -
- 3F
3H2F SbF5 SO2. 3F
(IV), -
-- -:
CH3F + SbF5 + SO2

CH3CH2F

SbF5
SO2 (.)

CH2=CH2 + CH3CH2F

CH3O-S=O SbF6

CH2=CH2 + HSbF6
SbF5
SO2 (.)

(CH3)3C SbF6

, SbF5 - FS3
-. -

. (CH3)3C+SbF6-
-20 .

, ,
. -2
-60 -

. -30 , -1
769

770

- .

:
(CH3)3C-OH

FSO3H - SbF5; (-60)-(-110 oC)

SO2 (.)

CH3 CH CH2CH3
OH
FSO3H - SbF5

FSO3H - SbF5
SO2 (.)
-110 oC

(CH3)3C

SO2 (.) ,-60 oC

(CH3)3C + H3O

CH3 CH CH2CH3
OH2
+ H3O

FSO3H - SbF5

(CH3)2CHCH2OH SO (.) (CH3)2CHCH2OH2

2
-60 oC

FSO3H - SbF5
SO2 (.)
-30 oC

FSO3H - SbF5

CH3CH2CH2CH2OH SO (.) CH3CH2CH2CH2OH2

2
-60 oC

(CH3)3C

FSO3H - SbF5
SO2 (.)
0 oC

+ H3O

(CH3)3C

+ H3O

3+23
(CH3)3C+-ao,
SO2FCl - SbF5, -14,5 /.
, - -. 1
:
X

SbF5

CH3
X

SbF5
SO2 (.)
-60 oC

X = Cl; OH

SO2 (.)
-60 oC

CH3

SbF5
SO2 (.)
-60 oC

XCH2

[3.3.0]-
:

770

771

Cl
SbF5
SO2FCl ;-78 oC

SbF6-; SbF5X-
-
.
-110
-, 40 -:
CH3CHCH2CH3
F

SbF5
SO2FCl
-110 o C

C H3CHCH2CH3
S bF 6

SbF5
SO2FCl
-40 o C

( CH3)3C SbF 6

-

, 10-15 /.

(. 9.10-9.12). ,

, .. 20 /. ,

, : > > .
-
: ,
, - , ,
, :
771

772

CH3O

SbF5 - FSO3H
SO2FCl; -78oC

CH2OH

C OH
H
CH3O

FSO3H; SbF5

CH2

CH

SO2; -60 oC

CH2CH2Cl

CH3O

SbF5

CH3O

SO2FCl; -78oC

SbF5

Br

SO2; -60 oC
1-

1-
SbF5

Cl

SO2FCl; -150 oC
2-
(. 9.7.4)

9.15
pKR+ 25 o

(n-Me2NC6H4)3C+

KR+

9,36

KR+
-0,84

( )
(n-HOC6H4)3C+

1,97

CH3

CH3

CH3

C(CH3)3

CH3

(n-MeOC6H4)3C+

-12,4

CH3

0,82
-16,6
CH3

(n-6H4)2C+64

-1,24

C
3

772

-2,3

773
(n-MeC6H4)3C+

-3,56

C6H5

C6H5

+3,1

C6H5

(5)3+

-6,63

C3H7-

-C3H7

+7,2

C3H7-

(n-FC6H4)3C+

+4,7

-6,05
( )
+

(n-ClC6H4)3C

-7,74

(n-NO2C6H4)3C+
(n-MeOC6H4)2CH
(n-MeC6H4)2CH

(C6H5)2CH+

-16,27
+

-5,71
-10,4
-13,3

(n-ClC6H4)2CH+

-13,96

-14,16

(n-BrC6H4)2CH

C6H5CH2+
2=-2+. , -
14 / -, 20 / , -.
- 3+ Ar2C+H
-.
.

.

-,
( 100%- 2SO4 H=-11,9):
ROH + 2H

H2SO4

R + H3O

R+
R+,

773

774

[R + ]
pKR+ = HR + lg
[ ROH ]

R+ -
ROH R+, HR -
( 2SO4 2; . . 3).
pKR+ R+, ROH
HR. R+
ROH , , ,
pKR+. pKR+
-, -,
, . 9.15.

9.7.3. ,

, . 9.11 - 9.15, ,

. ,
, ,
, , ,
.

9.7.3..

,
3+,
R3C+. <
<
. (. . 2)
p-

774

775

. ,
, :
H
H

H
H

C
H

(
-)

H
H

( )

(
3-
-)

(
-
-)

, ,

.
,
p-. ,
. - ,
- - ,
. , ,
. ,
3+ sp2-
, ,
3+ sp3-
, s- sp2- , sp3 .

(+I)- ,
( ,
, ).

775

776

, 5-, 7- 8- ,
. , ,
,
H

H2CH2CH2 C CH3
CH2CH2CH2 C CH3

CH3

CH3
.
,
. 1- (.
). , 1-
,
. 1 , -78 o .


(. 9.7.4.):

1-

, ,
, ,
, . ,

CH3OCH2+SbF6-.
p- :
+

(X = OR, NR2, Hal ..)

776

777

RCO+.
3+ , - (.
9.12):
R

, .. (R-C=O )

9.7.3.. ,

=-,
.
,
:
Nu:

:Nu

H
H

+1/2

+1/2

- , . 2,
, ,

.

1,3-; , 1,3--1,3 ,
:
H2SO4

CH3

CH3

+
CH3

CH3

, .
,

777

778

(. .
13).
:
H
H

H
H

H
H

H
H

(CH2=CH)3C

(CH2=CH)2CH

CH2
X

CH2

CH2
X

CH2
X

CH2

SbF6-
. - .
,
,
, S2 SbF5
FS3:
Ph3CCl

Ph3C

+ Cl

3+
,
54 , .
-
-.

778

779

-.
. 9.15 R+
- . ,
(OR; ; NR2), +-,
. ,
CN; N2 , -- -I, ,
R+.
50%-
. 4,4',4"-
4,4',4"- R+
ROH 2%- 88%- .
67 R+ ,
,
. ,
,
R+.
R+
, -
. . 9.14
R+ ,
(. 12).

9.7.3..

, () , (. .
9.14). ,
, .

779

780

.
,
2--2 96%- H2SO4
:
CH3
C OH

H2SO4

CH3

+ H3O

CH3

CH3

,
, , .. -
:
Me

MeMe

Me
H

14 /. ,

, (1),
(
. 2):
-(1)

(1)

(2)
(2)

(2)

(1)
(1)+

, :

780

781

, -, , -,
.

.
-

SN-.

9.7.3..

, ,
, -
(. 6). , ,

.
, ,
:
R1

R1
C C

R3

R3
C C

R2

R2

, , -
, , R2C=C(Z)Ar
SN1.

9.7.4.

781

782

,
,
-. ,
CH2=CHCH2+ ,
CH2=CH-CH2CH2+ , p-
-, :
1
2

4
3

p-
-, -,

-, p-
(4) p- (1) (2) .
- (1) (2) ,
,

. -, . 9.5
.
9.5

H

H
H
H

C H
H

H C
H

F
H

+
H

1--

782

783

H
+H

2--

CH2

H2C

7--

[3.1.0]

+
H

CH2

(, " ")

( ), -.

- (-),
- (-), :
-

Z
H H

,
:
R

H
C C H
R
R
OTs

R
C H
H

R C
R

( )

,

,
:
R
C C

(1) (2)

783

R
C

(1) (2)

784

R (1) (2)
, , ,
.

, .
, . 26 (. 3).
- ,
9.5, .
2. ,
- , . 26 (.
3).

784

785

10

10.1. .............................................. 785
10.2. -.............................................................................. 787

10.2.1. E1- ................................................................................................. 787

10.2.2. E1CB- .................................................................... 792
10.2.3. E2-. E2-.................................... 794
10.2.4. 2- .................................................................. 800
10.3.
.................................................................................................................... 810
10.4. .
................................... 815
10.5. ,
, ............ 819

10.1.
()
,
.
,
-. -
, :
R2

R2
R1

R1

C X

C: + HX

-
. 5 (. 1).
() ,
-. - :

R1

C R2

R1CH=CHR2 + HX

785

786

, ,
, , - ..
.
, ..
CH2

X-CH2-CH2-CH2-Y

CH2

CH2 + XY

,
, ..
- .
G = - S
S. -
- . , -
,
.
, -, -
CN, COOH, NO2
., :
ClCH2CH2CH2CN

NaNH2

CN + NaCl + NH3
67%

O
ClCH2CH2CH2 C CH2CH2CH2Cl

2NaOH
H2O, 50 oC

52%

+ 2NaCl + 2H2O

BrCH2CH2CH2Br

Zn, 80
C2H5OH

70%

+ ZnBr2

-,
.

786

787

10.2. -

- ,

- 1, 1 2.

10.2.1. E1-

1 ( ) ,
,
,
- ,

R1CH2CHR2

R1CH2CHR2 X

SolOH

R1CH=CHR2 + H2OSol + X ,
SolOH -

1

SNl (.9). , 1 SNl,
v = k1[RX],
, , , E1-. ,
, ,
:
(SN1) -
(1).
SNl - E1-
. SNl- E1 -

787

788

, ,
, :
80%EtOH-20%H2O
S N1

(CH3)3CCl

CH3
CH3CH2 C Cl
CH3

(CH3)3C-OH + HCl
(83%)

80%EtOH-20%H2O
E1

(CH3)2C=CH2 + H3O
(17%)

+ Cl

CH3

C2H5OH; 40 oC
S N1

CH3CH2 C OCH2CH3 + HCl

CH3

C2H5OH; 40 oC

(64%)

CH3CH2=C(CH3)2 + CH3CH2 C=CH2

E1

(30%)

(6%)

CH3

,
X, , ,
SNl 1 .
,
. ,
SNl/El
(. 9). , - (3)3S+(CH3)2 80% 65 o -
,
:
-,
65 , 4:1

(CH3)3CCl

-,
65 , 4:1

(CH3)3C-OH
(64%)

(CH3)2C=CH2
(36%)

-,
65 , 4:1
-,
65 , 4:1

(CH3)3CS(CH3)2

,
; SNl- 1 -

. , , (3)3 ,
, - 1 -
1 > Br > S+(CF3)2.

788

789

1 -,
,
, 1,2- -
. 3--2 80%- :
H OH
C C

CH3

CH3

H ,

H
H
H O
CH3

CH3H

C C CH3

Ha
C C CH2Hb

CH3

CH3H

CH3H

1,2-

-Hb

-a

H
CH2

C C

Hx

CH3Hy

CH3

CH3

CH3

C C CH3

CH3

CH3H

C CH CH2

-Hx

-Hy

CH2=C

(CH3)2C=CH-CH3

CH3
CH2CH3

E1-
3,3--2:
CH3CH3

CH3
CH3

C CH CH3 85% H3PO4 (CH3)2C=C(CH3)2 + CH2

100 oC

CH3OH

(CH3)3C CH CH3 + H

(80%)

(CH3)3C CH CH3

OH

H
CH3

CH3

C CH CH3

1,2- 3

CH3

CH3

C CH CH3
(20%)

H
H3
C CHa CH3
CH2 Hb

-Ha

(CH3)2C=C(CH3)2
(80%)

-Hb

CH3
CH2=C-CH-CH3
CH3 (20%)

789

790

1-
, .. ,
=-,
:
85% H3PO4
160-170 oC

+
CH3

OH CH3

(79-84%)

CH3

CH3
CH3CH2 C OH
CH3

45% H2SO4
90 oC

CH3CH2=C(CH3)2 + CH3CH2 C=CH2

(86%)

(14%)

CH3

1 ,
.

. (. 5)
, . , 1-
,
, , .
..
(1875) ,
1,
2- .

E1-. ,
.
, 1- 1,2--2-
5C(3)l-65 60% 2=(5)25,
, , 5(3)=65
.

. - -,
-. E1 .

790

791

l
1:2:
H3C

CH

H
H

H
CH3

CH3

H
H
Cl

H3C

4
3

CH(CH3)2 + H3C

1
2 3

CH(CH3)2

(68%)

(32%)

E2- l (.
) , -
(2)-(3).
, E1-,
--3- .
,
:
CH3
CH3CH2CH2

C CH2CH3

60 oC
CH3OH

CH3
CH3CH2CH2

C CH2CH3
OCH3

Cl
CH3
+

H
C

CH3CH2CH2

CH3

CH3CH2

CH3

CH3

CH3CH2CH2
H

CH3
+

H
CH3
+

CH3CH2

CH2CH3

CH3CH2CH2C CH2
CH2CH3

791

CH2CH3

792

, E1-
. ,
E2-.

10.2.2. E1cB-

1, 1, ,
.
:
B: + R1C CHR2
Y X

R1C CHR2 + BH
Y X

R1C CHR2 + X:
Y

,
, 1 ,
.
1

- : v = k[][-].
, ,
, . , 1-,
,
- ,
. ,
- , -,
- ,
,

R2CH(X)CH(R1)Y , Y=C(O)R; CN; NO2; SO2R; COOR, a X -

.
, 1B- ,
: F; N+(CH3)3;
S2F3 .
l2F3 ,

792

793

,
:

CHCl2CF3

CCl2CF3

-F

CCl2=CF2

1-
. , , ,
E1cB, E2-,
. E1cB-
,
. ,
,
:

l2=CHCl + OD

CCl=CCl

CCl + Cl

Cl

OD

CCl2=CCl

DCCl2

ClC

CF3

D2O
OD

CCl2=CDCl

OH , H2O

ClC CF2 F

Cl2C=CF2 + F

Cl

CCl2

CF3

H2O
OH

Cl2C CF3
H

- (. . 3,
. 1). , E1B-
Z-642-
, ..
793

794

. ,
,
, .
.
E1B-
-,

-. 3 ,
- .
,

> > ,
. , 3 , 2
-. , 1-

.

, .
,
, (CH3)3CO-K+; (C2H5)3CO-K+; (-C3H7)2NC2H5; Li+N-(C3H7-)2 .

.
1-
1-, .

10.2.3. E2-. E2-

2
. ,
() :

794

795

B
R1CH2

CHR2 + B:

CH3(CH2)3CHCH3 + (CH3)3CC
I

R2

H
R1

R1CH=CHR2 + BH + X

O
ONa

100

CH3CH2CH2CH=CHCH3 +
(94%)

+ CH3(CH2)3CH=CH2
(6%)

CH3CHCH2CH3 + C2H5ONa

C2H5OH
80 oC

Br
CH3(CH2)3CHCH3 + (CH3)3COK

CH3CH=CHCH3 + CH3CH2CH=CH2
(19%)

(81%)

(CH3)3COH
80 oC

Cl
CH3CH2CH2CH=CHCH3 + CH3CH2CH2CH2CH=CH2
(91%)

(9%)

:
, SN2. , : 2 SN2 .

:
SN2-,
2-.
E2-
. DBr
CD3CHBrD3 6,7 ,
r 33 , .. kH/kD= 6,7.
kH/kD 1 , ,
kH/kD = 3-8.
El, 1 2
, E2-
1 1. 2

795

796

.
,
.
E2-.
E2- ,
E2-, 1-
, , E1-. , E2- E1-
,
1-. . 10.1 ,
.

H-B

H-B

H-B

H...B

E1cB

+
X

E1cB-

1-

2-

. 10.1. 2

2-
.
E2-
1 1-.
, 1- E2- ,
.
, =
. , 1-,

. E2pe -

. E2-,
,
,
796

797

. , E2 .
E2-- 1- .
E2- 1 ,
,
.

, .
,
. , 10.2.1,
.
.
. ,
1851.,
. ,
, :
150 oC
H2O

CH3 CH2 CH CH3

N(CH3)3OH

CH3CH2CH=CH2 + CH3CH=CHCH3 + N(CH3)3 + H2O

(5%)

(95%)

CH3

120-150 oC
H2O

N(CH3)3OH

CH3

CH2 +
(99%)

(1%)

+ N(CH3)2 + H2O

E2.
, ,
,
. . 10.1

797

798

2- 2 2- .
10.1
E2-

% - % 1

3(2)2(X)-3
3-; 3

=I
=

19

81

25

75

3 ; 3

=1

3 ; 3

33

67

X=OTs

3-; 3

30

70

X=F

3 ; 3

69

31

X=I

(CH3)3CO-K+; (3)3

78

22

X=OTs

(CH3)3CO-K+; (3)3

83

17

X=Cl

(CH3)3CO K ; (3)3

91

X=F

(CH3)3CO-K+; (3)3

97

=N+(3)3

OH-; HOH

98

21

79

32(X)-3
(CH3)3CO-K+;

X=I

=r

(CH3)3CO K ;

33

67

X=Cl

(CH3)3CO-K+;

43

57

61

39

X=OTs
+

(CH3)3CO K ;
-

X=S (CH3)2

2H5 ; C2H5OH

74

26

X=N+(CH3)3

OH-; HOH

95

I < r < l OTs <S+R < F < N+R3, ..

,
. o I -
,
, , - , ,
. E2-
798

799

: F, N+R3, S+R2
1B-,
. ,
, ,
E2-
.
, .
10.1, -1/-2 1 2-
0,5 10, ..
- . 2--2-

- :
CH3
CH3CH2C

- +

CH3 + C2H5O K

80 oC
C2H5OH

Br

CH3

CH3CH=C(CH3)2 + CH3CH2
(71%)

CH3
CH3CH2C

C CH2

(29%)

- +

CH3 + (CH3)3CO K

Br

80 oC
(CH3)3COH

CH3

CH3CH=C(CH3)2 + CH3CH2
(28%)

C CH2

(72%)

.

. , , , -
, , --3 ,
., :

799

800

CH3

(CH3)3COK

Cl

CH3

CH2 +

(CH3)3COH
(75%)

(25%)

+ KCl + (C2H5)3COH

CH3
CH3CH2C

CH3 + (C2H5)3CO K

C CH2 +

CH3CH2

(89%)

Br
+

CH3

- + (CH3)3COH

CH3CH=C(CH3)2 + KBr + (C2H5)3C-OH

(11%)

10.2.4. 2-

E2-
. , p , ,
. -.
, , ( ,
, ), .
. ,
180 ( ), -, 0 ( ).
;
-.
,
.
. - ,
,
:

800

801

H
X

()

()

E2-
.
-
,
. , ()
() ( . . 24, .). -

, , , , ,
0 180:

a
a

e
a

eH
a

a
e

e
a

H a
H

- 6H11X , - , -

. , ,
X. ,
( - ).
-
.

, 2-.
- ,

801

802

, X,
,
. ,
, ( 4 / )
, , (. . 24, .). 2
:
CH(CH3)2

H
(CH3)2CH e

Cl

a e

CH3

aH
e

Cl

CH3

CH3
-

C2H5O Na

2-

C2H5OH

CH3

CH

CH3

,
-
2-
,
.

. (2) (4) .
l
3 : 1
, 3- 2-:

802

803

Cl
(CH3)2CH
4

CH3

H
1

CH3
2

5H5O Na

C2H5OH

CH3

H
(CH3)2CH
3-
(75%)

H
H

CH(CH3)2

2-
(25%)

1,2-
, , -,
.
1,1,2-,
82

. 82, -

,
, .
, -
, 82. 1,1,2--
- :
Br
Br*
H

Br*

Br
NaI
CH3OH

+ IBr*2

. .

([2.2.1]),
- 0, -
:

803

804

X
D
H

B:
-

+ X + DB

- ,

- 120 -
[2.2.1] , 180,
-. .
-
, - ,
180:
H
D

120 oC

N(CH3)3OH

+ N(CH3)3 + HOD

H
,
.
50% - 50% -.
-2-- -

- - 1
-, 3:
-

C 6H5 (CH3)3COK
(9%)

3-

(CH3)3COH
50 o C

H
C 6 H5

OTs

(CH3)3COK
(CH3)3COH
50 o C

C 6 H5

-2-

(91%)

1-

, 2- TsOH -2- 2-
TsOH -2- :

804

805

C6H5

(CH3)3COK; (CH3)3COH
50 oC

OTs

C6H5

- - ,
.
:
C

H C

C + ROH + KX

X
R

O....K

, ,
. , 1 3- - -2- 10 : 1
1 : 2,5 18-6 . 18--

(. . 11).

.
1-,
-.
, --
, - - . -
.
-

2---,

805

806

-. - 2-- ,

DBr.
:
CH3
H D

H Br
CH3

CH3

-2-3-

Br
CH3
D

- DBr

CH3

CH3

D
H

CH3

CH3

- HBr

--2

H Br
- DBr

CH3
D

--2

Br
CH3

CH3

H
CH3

CH3

CH3

--2

DBr
- DBr

CH3
CH3

H
H

CH3

CH3

--2

, 2---
--2, , -2. -.
-
2- .

,
, . 2- 3-, 3- -, 2-,

806

807

. . 10.2 2 -AlkX.
10.2
E2-

% -

% -

(3)3; (3)3

100

(3)3; (3)3

100

(3)3;

100

(3)3; (3)3

32

68

(3)3; (3)3-

20

80

(3)3;

38

62

(3)3; (3)3

93

(3)3;

24

76

(3)3; 66

20

80

CH3CH CHCH3
D Br
CH3CH CHCH3
D OTs
CH3CH CHCH3
D N(CH3)3
CH3CH2CH CHCH
CH2CH3
D F
CH3CH2CH CHCH
CH2CH3
D N(CH3)3

CH3(CH2)3CH CHCH
( 2)3CH3
D Cl

CH3(CH2)3CH CHCH
( 2)3CH3
D OTs

CH3(CH2)3CH CHCH
( 2)3CH3
D N(CH3)3

CH3(CH2)3CH CHCH
( 2)3CH3
D

, . 10.2, -

- ,
- . , 2- - -.

807

808

, -10.
- -
(-5)-.
C4H9

C4H9

C4H9 H

C4H9

(CH3)3COK

CH3(CH2)3 CH CH2(CH2)3CH3

(CH3)3COH

N(CH3)3

,
, - ,
.
(-5)- - ,
- -.
(CH3)3N
C4H9
H

H*

C4H9

H
C
4H9
A

(CH3)3N

C4H9
C4H9

-,
62%

H*
H
H

-,
9%

C4H9

C4H9

(CH3)3N
H
C4H9

-,
2%

C4H9

-,
23%

C4H9
H*

(CH3)3N
C4H9
C4H9

H
H*

, 90% --5 .
, --5 ,
. 2-, , .
,
. -
- ,
10

dichotomy -
808

809

- , .

, - ,
-, --
, --.
, , ,
- -.

, - , -
- R1CHX(HaHb)R2 :

R2
R1

X
Ha

R1
Ha

Hb

- HbX

R2

Ha

R1

Hb

R1

Ha

R2

- HbX

H
R2

- -
,
. , ,
- ()
- -.
-

(20 = 49) , -.
-
R1R2CHCHDN+(CH3)3OH-, R1 R2
- . ,
-,

809

810

, -.
-:
(CH3)3N

H
R2

(CH3)3N
R1

H*

D
R1

H*

R2
D

- -, ,
,
.
,
.
- ,

, , -, -,
- -, - --
. -
, -,
, :
O
Br

LiCl
, 80

O
(76%)

CH3
(CH3)3CCOOK

CH3(CH2)2CH CH3 , 100

Br

CH3

CH3(CH2)2 CH CH CH3
(95%)

10.3.

810

811

- - .

, . , , 2- 2 -1, - --2 2 SN2- :
C2H5O K

CH3CHCH2CH2CH3
Br

CH2CH3

CH3

CH2=CHCH2CH2CH3 +

C2H5O; 60

(25%)

CH3

H (41%) CH2CH3

H (14%) H

+ CH3CHCH2CH2CH3 + KBr + CH3CH2OH

OC2H5

(20%)

R1CH2CHXR2 - -:
R1

R2

R1

B:

R1CH2CHR2

+
H

+ BH + X:
2
R

X = F; Cl; Br; I; OTs; OSO2R

K E2-.
- - , - -

:
X
R
R

H
H

R
B:

+ HB + X:

X
R

R
H

B:

+ HB + X:

811

812

, ,
,
. -
, -
R. ,
2-
- --2 3:1, 1,4-

-2- 50:1.
-- - , 4:1

5:1.

, - -
-2-.
.

--

I > > 1 > F.
CH3CH2CH2CH2HCH3
X
CH3CH2CH2
+

CH3O; 60

H
(2)

CH3O K

CH3(CH2)3CH=CH2
(1)

CH3CH2CH2
+

CH3

CH3
(3)

(1),%

(2),%

(3),%

=I

19

63

18

=r
=l

27
33

56
50

17
17

X=F

69

21

10

2- -
-- -2
3,5 2,1 , .
,

812

813

: (3)3, (25)2
LiN[CH(CH3)2]2.

-1 . ,
--
-2:
(CH3)3COK

CH3CH2CH2CH2HCH3
X
CH3CH2CH2
+

(1)

CH3CH2CH2

H
(2)

CH3(CH2)3CH=CH2

(CH3)3CO

CH3

CH3

(3)

(1),%

(2),%

(3),%

=I

78

15

X=Cl

91

X=F

96

2-
- --2, 2- -2 -

, --2.
- -

.
(. 8)
: - (
R-, S-) - (
-). R1CHXCHXR2 -
-. -
-, - - -. -
- ,

-:
X
H

R1
R2

R2
B:

B:

R1

813

X
H

R2
R1

814

- -
, R1 R2 :
X

R2

R2

R1

B:

R1

, ,
r 2---. r 2-- --2. r (R,
R)- (S, S)- ()-

, (R, S)- (S, R)-- (Z)--2:

H
CH3CH2
CH3

R,R-

Br

CH3

CH3

CH3
CH3CH2

H
S,S-

H
CH3
CH3CH2

CH3CH2O

CH3

H
CH3

()-3--2

Br

CH3CH2O

CH3
CH3

CH3

CH3CH2
CH3

H
R,S-

CH3CH2

Br
H

S,R-

CH3CH2O

CH3CH2O

CH3CH2

H
CH3

(Z)-3--2

Br

- -
, -:

814

815

(CH3)3N
R1
H

H
H
R2

R1

R2

R2

R1

(CH3)3N

R1

R2

H
H

10.2.4 (-5), - -
30 , - -
, . , -
.

10.4. .


Y:
,
.
. El- SNl- . ,
E1 - SNl
.
1- - ,
SN1-
.
- . ,

, .. SNl > E1,
.
,
1

815

816

2. SNl- E1 ,
, , ,
FSO3-SbF5, SO2ClF-SbF5 ,

.
SN2- E2-
,
RX , .
E2-,
- SN2-:
CH3CH CHCH3

LiCl

CH3CH CHCH3 +

CH3 Br

CH3C CHCH3
CH3

CH3 Cl

(50%)

(50%)

CH3CH CHCH3

(H3)3CO K

CH3CH CHCH3 +

CH3 Br

CH3C CHCH3
CH3

CH3 Cl

(89%)

(11%)

CH3CH CHCH3
CH3 Br

C2H5OK
C2H5OH, 80 oC

(CH3)2C CHCH3
(99%)

--2--.
- -2- SN2-
, - -
.
, (3)3, (2H5)3, (-37)2NLi -

, RX E2-
:
CH3CHCH3
Br

C2H5ONa
C2H5OH

CH3CH CH2 + CH3CHCH3

(87%)

816

(13%) OC

2H5

817

CH3CHCH3 (H3)3CO K
(H3)3COH

Br

CH3CH CH2
(98%)

,
:
CH3
CH3CH2CCH3
Br

(2H5)3CO K
(2H5)3COH

CH3CH C(CH3)2 + CH3CH2C CH2

(11%)

(89%)

CH3

,
,
- ,
:
O
Cl

LiCl
, 80-100

O
CH3

CH3

() .
,
-
sp3-
, 2-
:
CH3(CH2)2CH2CHCH3 + (CH3)3CCOONa

100 oC

I
CH3(CH2)2CH=CHCH3 + CH3(CH2)3CH=CH2 + NaI + (CH3)3CCOOH
(94%)

(6%)

, ,

817

818

, , (-37)2Li22
:
-C6H13CH2CH2Br

(-C3H7)2NC2H5, 180 o

CH3

CH3

[(CH3)2CH]2N Li
, 60

CH3CHCH2CH2CH2Cl

C6H13CH=CH2 (99%)

CH3CHCH2CH=CH2
(87%)

1,5-[4,3,0]-5 ()
1,8-[5,4,0]-7 ():
N

N
1,5-[5.4.0]-7 ()

1,5-[4.3.0]-5 ()

-
,
SN2-:
-C18H37Br

(H3)3CO K
(CH3)3CO; 80

-C18H37OTs

-C16H33CH=CH2 + -C18H37OC(CH3)3
(85%)

(H3)3CO K
(CH3)3CO; 80

(15%)

C18H37OC(CH3)3
(99%)

SN2- 1 -.
-
2-
< < (. 9, . 1).
- E2 SN2-.

- . ,
. 10.3, 2- SN2-
.
818

819

- , . 10.3,
E2-, SN2-
, 1-
. -
E2-,
522 55
1- .
10.3
- - .
SN2- 2-

% SN2-

% 2--

33r

55

99,1

0,9

333r

55

91

3333r

55

90

10

(3)3r

25

19,7

80,3

(3)23r

55

40

60

(3)3r

25

100

33-(Br)-23

25

12

88

3(CH3)-(Br)-3

55

95

SN2- 2-
.

.

10.5.
, ,

,
, .

819

820

,
. , ,
400-600o -
:
C

O
O

400-600 oC

+ RCOOH

C R

i
,
.
. 25 (. 4).

.

, ..
- . , , - 55-62% -1 38-45% -2,
3:2 :
O
CH3C O CH CH2CH3

500 oC

CH3CH2CH=CH2 +
(55-62%)

CH3
+ CH3CH=CHCH3 + CH3COOH
(38-45%)

-
- -
.
-
-. ,

, -
, -
. -
820

821

,

65:35,
- l
, 2:
CH3
CH CH3

H
H

500 oC

H
H

H
CH3

CH3
(65%)

C O
CH3
+ CH3

(35%)

CH3
+
CH
CH3

CH3
CH
CH3

,
- .

,
, :
AcOCH2(CH2)3CH2OAc

575 oC

CH2=CHCH2CH=CH2 + 2CH3COOH
(63-71%)

CH2OAc

CH2OAc

CH2

CH2OAc

550 oC

+
CH2

(1:3)
(94%)

CH2

-1

:
-C18H37OH + (CH3CO)2O

600 oC

-C16H33CH=CH2 + 2CH3COOH
(68%)

821

822

,
, .
1899 . .. .


. 130-200o
, COS 3S:
CS2
NaOH

H O C

H OH

130-200 oC

CH3I

S
H O C

SNa

SCH3

+ COS + CH3SH

C C

, ,
> > .
.
-
. s - -1,2--1
- --:

CH3

C6H5

C6H5 H OHH

1) CS2, NaOH
2) CH3I

C6H5
H
O

CH3
C6H5
H

C
SCH3

150-190 oC

CH3
C6H5

C6H5

O
+

HS

C
S

CH3

t oC

--

OS + CH3SH

822

823

CH3

1) CS2, NaOH

C6H5 H OH6H5 2) CH3I

CH3
C6H5
H

H
6H5
O
S

C
SCH3

C6H5

CH3

150-190 oC

C6H5

+ OS + CH3SH

--

S-
, ,
.
,
:
CH3 H
CH3

150 oC

C CH3
CH3 O C

(CH3)3CCH=CH2 + COS + CH3SH

(58%)

SCH3

S
S
O

150-190 oC

+ COS + CH3SH

SCH3
CH2C6H5

(95%)

CH2C6H5

N- . (1949):
R12CH CH2N

R2
2

22

RCO3H

100-150 oC 1
R12C CH2
R 2CH=CH2 + R22N-OH
H
N R22
O

N,N-
- i
. N- 100150 - ,
.

823

824

-, ,

:
O
CH2N(CH3)2

CH2 N

CH3
CH3

H2O2

H2O-CH3OH, 20 oC

CH2

150 oC

+ (CH3)2N OH
(80-88%)

1-.

- -,
, ,
.
. . (1963).
(
) .
(1,2-) (N,N)
:
+

C C
HO

OH

C N

150 oC

C
O

C
C

C
O

C
C

+ P(OR)3

110-120 oC

(75-95%)

824

NH

+ (RO)3P=S + CO 2

825

-,
, :
-C4H9

H C
HO

-C4H9 1)
C H

C N

-C4H9

2) P(OCH3)3

OH

-C4H9
+ (CH3O)3P=S + CO2
H

(92%)

, , 1,2. -
1,2- :
CH3

CH3

P(OC4H9)3
115-120 oC

CH3
CH3

+ (CH3O)3P=S + CO2
(63%)

, , , - -
:
(H3)3COK

S O

(H3)3COH

+ RSO2 + (CH3)3COH

+ RSO2 + (CH3)3COH

R
CH3CH2O Na

SO 2
R

.
, - C(O)R, COOR
CN-, -
(. . 17) ,- ,
:
O
O
o
20-60 C
R1C CH CHR2 + C6H5SeOH
R1C CH CHR2
Se H
C6H5

825

826

- .
SNi-
SO2 :

RCH2SO2CHR

OH

RCH

Cl

RCH

CHR
SO2
Cl

CHR
SO2

RCH=CHR + SO2

.
(. 5, . 1)
,
3
.
-, . ,
-1
, :
RCH=CHCH3

BH3

(RCH2CH)3B

t oC

RCH2CH=CH2 + BH3

CH3
, ,
.
R2CH=CH2 RCH2CH=CH2
:
RCH2CH2CH2BR12 + R2CH=CH2

t oC

RCH2CH=CH2 + R2CH2CH2BR12

, , 1- -
:

826

827

CH2CH3

CH2CH3

BH3

3B

CH=CH2

-C8H17CH=CH2
t oC

CH2CH3
+
2B

(62%)

827

CH2CH2C8H17-

828

11.
, ,
11.1. ................................................................................................ 829
11.1.1. ...................................................... 830

11.1.2. ................................................................. 831

11.1.2.. .......................................................................................... 831

11.1.2.. - ........................ 832
11.1.2.. ....... 832
11.1.2..
............................................................................................... 833
11.1.2..
.......................................................................................................... 834
11.1.2..
......................................................................... 835
11.1.2.. ()
...................................................................................................... 836
11.1.2..
....................................................................................................... 837
11.1.3. .................................................................... 838

11.1.3.. - ................................................................. 841

11.1.3.. .
............................................................................................................ 844
11.1.3.. ..................................................................................... 861
11.1.3.. ...................................... 865
11.1.3.. ........................................................................................... 867
11.1.3.. ............. 879
11.2. ................................................................................................ 882

11.2.1. .................................................................................................... 883

11.2.2. ....................................................................................................... 887

11.2.2.. ........................................................................................................ 887

11.2.2.. 1,2- ............................................. 892
11.3. ................................................................................................................ 896

11.3.1. ........................................................................ 896

11.3.2. ................................................................................ 897

11.3.2.. .......................................... 897

11.3.2.. ............................................................ 898

828

829

11.3.2.. . ............................................ 899

11.3.3. ................................................................................... 901

11.3.3. ........................................... 903

11.3.3.. ................................................. 905
11.3.4. () ............................................................................................. 906

11.3.4.. ..................................................................................... 907

11.3.4.. ......................................................................................... 908
11.4. ....................................................................................................... 914

11.4.1. .................................................................................................... 916

11.4.2. ....................................................................................................... 917

11.1.
,
.
, ,
.. ,
,
.
. 11.1.
H

H C
H

, 1,10

, 109

, 0,96

, 110

, 1,43

, 109

.11.1.

109 110 sp3-

, . O ,
. sp3 .

829

830

11.1.1.
,
. ,
ROH :
CH3CH2CH2CH2OH

CH3

CH3CHCH2OH
CH3

CH3

C OH
CH3

BrCH2CH2CH2OH

CH3OCH2CH2OH

,
, -- Br(CH2)nOH.
.
, , 3
. ,
:
CH3CHOH
C2H5

CH3

C OH
CH3

CH3

CH3

C6H5

C OH
CH3

,
, , ,
.
,
, , . .

830

831

, ..
.
, -.
, . ,
, ,
-:
CH3

CH3
CH3

CH3 CH CH CH2OH

C CH CH CH3
CH3CH3 OH

CH2CH3

3,4,4--2

2--3--1

CH3

CH3
CH3 CH CH CH2OH
CH2CH2Cl

OH
-3 -

4--2--1

. 2 :
CH2OH

HO
CH2OH
-(3-)

11.1.2.

11.1.2..

-
-2 (. 5, . 1).

,

831

832

(. . 5, 9),
, .
.
, .

11.1.2.. -

.
,
, ( . . 5, I):
1) (CH3COO)2Hg; -H2O

CH3(CH2)3CH=CH2 2) NaBH4; H2O

CH3(CH2)3CHCH3
(96%)

OH

OH

1) (CH COO) Hg; -H2O

3
2
CH3 2) NaBH
4; H2O

(92%)

CH3

11.1.2..

5.
,
:
CH3CH2C=CH2
CH3
CH3(CH2)4CH=CH2

1) BH3;
2) H2O2; NaOH

1) Sia2BH;
2) H2O2; NaOH

832

CH3CH2CHCH2OH
CH3

99%

CH3(CH2)4CH2CH2OH 99%

833

11.1.2..

(LiAlH4 NaBH4)
, .
.
,
, ,
120 :
O 1)NaBH ;
4

CH3(CH2)3C

2) H3O

(85%)

1)NaBH4;

HO

CH3(CH2)3CH2OH

CHO 2) H O
3

HO

CH2OH (93%)
H

1)NaBH4;
2) H3O

OH

OH

O
1)LiAlH4;
2) H3O

O
(C6H5)2CHC
CH3

(88%)

CH3
CH3

LiAlH4

(90%)

(C6H5)2CHCH2OH
(97%)

CH3
O

CH3
CH3

1)LiAlH4;
2) H3O +

OH

(95%)

H
-

0-10 o ,-
, .. .
:

833

834

1)LiAlH4;
0-10 oC
2) H3O + 0 oC

OH
+
(94%)

CH CH CHO

(6%)

1)LiAlH4;
0 oC
2) H3O + 0 oC

OH

CH CH CH2OH
(90%)

-2- NaBH4 2- 1,5 : 1

- ,
- :
OH

1) NaBH4,
2) H3O +

H
+

(59%)

(41%)

OH

,- ,

- (.16, .),
(-):

-
, 10

(90%)

11.1.2..

.

. ,
.

834

835

NaBH4 .
80%.
:
O
1)LiAlH ;
C6H5CH2OH + C2H5OH
C6H5 OC2H5 2) H O+4
3

(90%)

1)LiAlH

CH3CH2CH=CHCOOC2H5 2) H O+4
3

CH3CH2CH=CHCH2OH + C2H5OH
(91%)

o
CH3(CH2)14COOC2H5 1)LiAlH+4; ; 65 CCH3(CH2)15OH + C2H5OH
2) H3O

CH2COOH

(95%)

1)LiAlH4; ; 36 oC

CH2CH2OH

2) H3O

(97%)

CH3(CH2)7

CH3(CH2)7CH=CH(CH2)7COOH

1)LiAlH4; ; 65 oC
2) H3O +

O
C

(CH2)7CH2OH
H

(87%)

Z-9--1-

CH3

C=C

OH
NaBH4
CH2CH2COOC2H5 1)
2) H3O+

CH3

C CH2CH2COOC2H5

(85%)

,
(. 16, . 3).
-,
s2 sp3:
R

C O
R

O
C

H3O

OH
C

+ H2O

11.1.2..

835

836

.
. . 19 (. ):
1)CH O; ;

MgBr 2) H 2O
3

CH2OH
(65%)

O
(CH3)2CHCH2

1)PhMgBr; ;
2) H3O

(CH3)2CHCH2 CH Ph (73%)
OH

CH2CH3

1)CH3CH2MgBr; ;
2) H3O

(89%)

OH
OH

CH3(CH2)3COOC2H5

1)CH3MgBr; ;
2) H3O

CH3(CH2)3(H3)2
(85%)

11.1.2.. ()

LiAlH4
. -

.
-.
C6H5CH CH2

1) LiAlH4;
2) H3O

C6H5CH CH3
OH

H
(CH3)3C

1) LiAlH4;

2) H3O

(CH3)3C
OH

836

837

CH3

H
C

CH3

1) LiAlH4;

C
CH3

2) H3O

HO
CH3
CH3

CH3
D

(. 19, . 3). -2
:
H
O

1) ;
2) H2O

+ (CH3)2Cu Li

OH
CH3
H

11.1.2..

2 18--6 :
18--6

RX + KO2 ; 25 oC

ROH (35-75%)

,
, , .
-1 -2 1- 2 :
CH3(CH2)6CH2I + KO2

18--6
; 25 oC

CH3(CH2)6CH2OH + CH3(CH2)5CH=CH2 + CH3(CH2)6CHO

(12%)

(3%)

(63%)

CH3(CH2)5CHCH3 + KO2

18--6
; 25 oC

CH3(CH2)5CHCH3 +
(48%)

+ CH3(CH2)5CH=CH2 + CH3(CH2)4CH=CHCH3
(48%)

837

OH

838

(CH3)3C

OTs + KO2

18--6
; 20 oC

(CH3)3C

OH
(95%) -

,
(S)--2 (R)--2 9799%:
C6H13
H

1) KO2;18--6;

OTs 2) H O
2

C6H13
HO

H
CH3

CH3

ROOR.
(II)
(-) , ,
(III) (. 28, . ):
CO + 2H2

Cu-ZnO-Cr2O3
250 oC, 50-100

CH3OH

,
(. 28, . 3):
2CO + 3H2

Rh Ru

HOCH2CH2OH

11.1.3.

.
150 , ,
. 123 ,
.. , 104 ,
(. 11.1).
.

838

839

,
,
.
R

H O

H O H O

R
H

H
R

H O

11.1

-97

64,5

0,79

32

-114

78

0,78

-1

322

-126

97

0,80

-2

3()3

-89

82,5

0,79

-1

CH3(CH2)3OH

-90

117

0,81

-2

3()23

-115

99,5

0,81

2---1

(3)22

-108

108

0,80

2---2

(3)3-

25

82

0,79

-1

3(2)4

-79

138

0,82

-2

3()223

119

0,81

52

113

0,81

(-
)

2,2-- (3)32
1 (-
)

-59

-19

141

0,95

-1

3(2)5

-52

156

0,82

-611

25

162

0,96

-1

3(2)6

-34

176

0,82

-1

3(2)7

-16

194

0,83

-1

3(2)8

-6

214

0,83

839

840

-1

3(2)9

233

0,83

-2--1

H2=CH-CH2OH

-129

97

0,86

C6H5CH2OH

-15

205

1,05

(65)2

69

298

(65)3

162

380

22

-11,5

198

1,10

1,2-

3()2

-8

188

1,07

HO22CH2CH2O

-10

245

1,12

HO222CH2-

285

1,12

( )

( )

()

. 11.1
1

()

-CH2CH2O

2()2

18

290

1,26

CH3OCH2CH2OCH3

-58

85

0,86

3O(22O)23

-64

162

0,93

3(22O)33

-45

218

0,98

3O(22O)43

-30

275

1,01

-108

65

0,88

-90

135

0,93

(1,2,
)

()

()

()

C2H5OCH2CH2OH

840

841
()

322

-85

124

0,96

CH3O(CH2CH2O)2H

-70

194

1,01

12

101

1,03

-37

154

0,99

()

1,4-

653

11.1.3.. -

,
.
(. 3)
(3)3 > (3)2 > 32 > 3 > 2,

:
H2O > 3 > 32 > (3)2 > (3)3.
. 11.2 a ,

.
- , , . - a ,
, (H3)3
.
2-, 2,2,2-
(-I) . .
11.2 2-.
G1o 2- , G2o
(G1o > G2o), Ka(32) > Ka(FCH2CH2OH).
, Go = -RTlnK, Go

841

842

. ,
,
. 2-

C+F

+ CH 2
CH 2 O -

C+F ,
.
,
F22O- 32-.
11.2

Ka.

R
(3)3-

18,0

(3)2

17,1

32

15,9

15,5

15,7

ClCH2CH2OH

14,3

FCH2CH2OH

13,9

CF3CH2OH

12.4

F322

14,6

F3222

15,4

(CF3)3COH

5,4

842

843
. 11.2. 2--

2-
FCH2CH2OH 32. ,

2,2,2-.
,
, , 3--
, 2-.
, -, -I-,
, -, +I-.
, Ka
, (. 11.2).
- ,
+I- , ,
-

.

, -- (. 3, . 1),
--
-
.
-- ,
, ,
:
(3)3 + (3)3 + H2,
(3)2 + 1 [(3)2]3l + 2,
3 + Mg (CH3O)2Mg + 2.
,
.
,
, .. .
-

843

844

,
.
. ,
,
.. ,

.

11.1.3.. .

,
.

.
,
.
,
.

ROH + HHal RHal + 2O

HI >
HBr > HC1 >> HF. HF
.
> > .

0-10 ,

0-20 o.
,

844

845

.
r HI
.
7590%:
CH 3CH 2CH 2CH 2OH

48% HBr + H 2SO 4, 120 o C

2

CH 3

CH 3
+ H 2O
Cl

(90%)
HCl; ZnCl 2

CH 3(CH 2)4OH

CH 3CHCH 2CH 3

(95%)

H Cl ()
, 0

OH

(CH 3)3COH

CH 3CH 2CH 2CH 2Br + H 2O

CH 3(CH 2)4Cl + H 2O

H 2O

(76%)

HCl; H 2O, 20 o C

(CH 3)3CCl + H 2O

10

(94%)

NaBr + . H 2SO 4, 60 o C

CH 3CHCH 2CH 3 + Na HSO4 + H 2O

OH

Br

HOCH 2CH 2CH 2CH 2CH 2CH 2OH

KI + 85%H 3PO 4
80 o C

(60%)

I(CH 2)6I + KH 2PO4 + H 2O

(78%)

.
- :
ROH + HBr

RO H

2Br

. SN2-
:
Br

+ RCH 2OH 2

+ RCH 2OH 2

SN2

SN2

RCH 2Br + H 2O

RCH 2I + H 2O

845

846

- -.

- .
.
,
-:
RCH 2OH + ZnCl2

RCH 2 O

H
ZnCl2

Cl

CH 2 O
R

RCH 2Cl + Zn(OH)Cl2

ZnCl2

6H52 > 2=2O > R3- > R2CHOH >
RCH2OH.
, -,
SNl
.

, , - -:

R 3COH + H
Hal

R 3C-OH 2

R 3C + H 2O

R 3CHa l + H 2O

, -,
.

.
-
. 1,2- .
,
, 1,2-
:
846

847

H
H

, , --2,
,
2--2- 2--- .
,

1,2- :
HBr; 0-20 o C

CH 3CH CHCH 3

CH 3CH CHCH 3

OH CH 3

OH 2 CH 3

-H 2O

Br

H
CH 3CH 2

CH 3CH CCH 3

CHCH 3

Br

CH 3CH 2CHCH 3
(64%)

CH 3

CH 3

CH 3

,
. - -2,
-3 2- 3-,
. -,
.
CH 3CHCH 2CH 2CH 3

H Br

OH

CH 3CHCH 2CH 2CH 3 + CH 3CH 2CHCH 2CH 3

Br

CH 3CH 2CHCH 2CH 3

H Br

OH

(86%)

Br

(14%)

CH 3CHCH 2CH 2CH 3 + CH 3CH 2CHCH 2CH 3

Br

(20%)

Br

1,2-

CH 3CHCH 2CH 2CH 3

CH 3CH 2CHCH 2CH 3

Br

Br

CH 3CHCH 2CH 2CH 3

CH 3CH 2CHCH 2CH 3

Br

Br

847

(80%)

848

1,2-
-, ,
. , ,
,
-.
2--2-:
(CH3)3CCH2OH + HBr

(CH3)2CCH2OH2

(CH3)2C

CH2
CH3

CH3
-

Br

(CH3)2CCH2CH3

(CH3)2CCH2CH3
Br

CH 3
(CH 3)3C

CH

(CH 3)3C

OH

1,2-H 3-

CH 3
CH 3

CH 3

OH 2
CH 3
CH 3 C

C CH 3

CHCH 3

CH 3
Br CH 3

Br

CH 3 C

CH 3 H

C CH 3

CH 3 H

-1 1-
, , , SN2-.

:

CH 3CHCH 2OH

H Br, H 2SO 4
100 o C

CH 3
CH 3CHCH 2Br + CH 3 C

CH 3

CH 3

(80%)

Br

CH 3

(20%)

,

--1.
, ,
.

848

849

: r3; l5; 13 I3,

.

:
3 ROH + r3 3 RBr + 33.

, .

r3 I3
-
- -
2.

:
RCH 2OH + PBr 3

RCH 2 O

PBr 2 + Br

H
Br

+ RCH 2 O

PBr 2

RCH 2Br + HOPBr 2

H
2
,
r3 I3
:
(CH 3)2CHCH 2OH + PBr 3

, 0

(CH 3)2CHCH 2Br

(60%)

, 37

CH 2OH + PBr 3

CH 2Br
(80%)

r

, .
r3, I3, l5, l3
849

850

. ,
,
,
. -3
85% 3- 15% 2- - . -2
,
. ,
, :
CH 3CH 2CHCH 2CH 3

PBr 3
, 0

CH 3CH 2CHCH 2CH 3 + CH 3CHCH 2CH 2CH 3

Br (85%)

OH

CH 3CHCH 2CH 3
CH 3 OH

PBr 3
, 0

CH 3
CH 3CHCH 2CH 3 + CH 3CH 2 C
CH 3

PBr 3

Br

CH 3

Br
(90%)

(10%)

(CH 3)3CCH 2OH

(15%)

Br

(CH 3)3CCH 2Br + (CH 3)2C(Br)CH 2CH 3 + CH 3CH(Br)CH(CH 3)2

(63%)

(26%)

(11%)

, , , , N,N, r3, I3, l5, 13

, . ,


.
, .

70-90%.
SOCl2
. :
(, ,
):

850

851

ROH + SOCl

,
2

RCl + SO

+ HCl

,
SNi
.

SNi ,
SO2. ,

:
R1

R1

H
*
OH

R2

+ SOCl2

R1

H
C*

R2

O
Cl

S O

R2

Cl

+ SO2

. ,
, , SNi
-,
:
R1

O
CH

R2

S
Cl

R1

R1

CH Cl + SO2

CH OSOCl
R 2

R2

2-
SNi . 2- 78%-

,
- .
2-
84%,
.

:

851

852

O
O

O + R

SN2

S Cl

O R + Cl + SO2

- :
l + RO

SN2

RCl + O

.
.


.
O-S(O)-Cl
- . -
, ,
:
R1

R2

+ SOCl2 +

R1
Cl

OH

R2

H
O

,
-10

R1
R2

,
-10

Cl

O +
S

NH Cl

Cl

Cl

R2

+ SO2 + Cl

R1

, , (PCl5, AsCl5, l3, r3,
POCI3 .)
.
,
.


0 ... -10 o

852

853

r3 l5
, :
(CH 3)3CCH 2OH

CH 3CH CHCH 3
OH CH 3

SOCl2

(CH 3)3CCH 2Cl + (CH 3)2CCH 2CH 3

(58%)

SOCl2
CH 3CH

, -20

Cl

Cl

CHCH 3 + CH 3CH 2

C(CH 3)2

CH 3

Cl

(80%)

(20%)

CH 2OH
CH 3O
CH 3CH COOC 2H 5
OH

SOCl2

, -20

SOCl2

-10

(42%)

CH 2Cl
CH 3O

(91%)

CH 3CH COOC 2H 5
Cl
(95%)

- .
, N.
-
.
. .
,
.
(5)3.Br2 (5)3.l2
:
(CH3)3CCH2OH + (C6H5)3P.Cl2

150 oC

853

(CH3)3CCH2Cl + Ph3PO + HCl

(92%)

854

CH3
CH3CH CHCH3 + (C6H5)3P.Br2

CH3

75 oC

CH3CH CHCH3 +

OH

Br

(44%)

CH3
+ CH3CH2CCH3 + Ph3PO + HBr
(1,5%)

Br

+ (C6H5)3P.Br

150 oC

OH

(62%)

CH3

+ Ph3PO + HBr

Br

CH2OH
+ (C6H5)3P.Br

CH3

150 oC

CH2Br

+ Ph3PO + HBr

(70%)

-

.
-
, :
Br
ROH + (C6H5)3P

Br

RO

P(C6H5)3Br + HBr

Br

+ ROP(C6H5)3

RBr + Ph3P=O

,
,
.

:

854

855

CH2Cl2, 0 oC

CH3CH(CH2)5CH3 + (C6H5)3P + CBr4

OH

CH3CH(CH2)5CH3 + Ph3P=O + CHBr3

(90%)

Br

CCl4
80 oC

+ (C6H5)3P + CCl4

+ Ph3PO + CHCl3

Cl

(57%)

OH

CH3

CH3

CH3

OH

CH3
CH3

+ (C6H5)3P + CCl4

CH3
Cl

(82%)

+ Ph3PO + CHCl3

CH2Cl

CH2OH
HO CH
O

+ (C6H5)3P + CCl4
O

CCl4

HO CH
O
C6H5N
0 oC

O
(96%)

CH3

+ Ph3PO + CHCl3
CH3

CH3

CH3

.

. l3-
, - (. 3, . I):
+

Ph3P + ClCCl3
Ph3P

Ph3P ... Cl ... CCl3

Cl

Ph3PCCl3 Cl

CCl3

855

856

:
+

Ph3P Cl CCl3

Ph3P ... Cl ... CCl3 + ROH

R

Ph3POR + CHCl3 + Cl
-

:
Cl + ROPPh3

S N2

RCl + Ph3P=O

,
. h3+R l-
- .

Ph3P(Cl)-OR

, - -, .
.

, l4.
h3+R l-, CCl4,
(. 16, .
3) :
Ph3P

+ Ph3PCCl3 Cl

Ph3P=CCl2 + Ph3PCl2

:
Ph3P=CCl2 + Ph3PCl2 + ROH

Ph3PCHCHCl2 Cl + Ph3POR Cl

856

857

Rh3PCHCl2 Cl + Ph3P
ROH

Ph3P=CHCl + Ph3PCl2

Ph3PCH2Cl Cl + Ph3POR Cl

Ph3POR + Cl

S N2

RCl + Ph3P=O

.


.
> > .

.
.

,
(C6H5)3P l325 (C6H5)3P
CCl3CN, :
CH3CN

CH3(CH2)4CH(CH2)4CH3 + P(C6H5)3 + CCl3COOC2H5 0-20 oC

OH
CH3(CH2)4CH(CH2)4CH3 + Ph3P=O + CHCl2COOC2H5
(83%)

Cl

CH3 CH CH (CH2)4CH3 + (C6H5)3P + CH3CN

CH3 OH

CH3CN
20 oC

Cl

CH3 CH CH (CH2)4CH3 + CH3 C

CH3 Cl (40%)

(CH2)5CH3 +

CH3 (0,1%)

+ Ph3PO + CHCl2CN
(CH3)3CCH2OH + (C6H5)3P + CCl3COOC2H5

90 oC

(CH3)3CCH2Cl +
(95%)

+ Ph3PO + CHCl2COOC2H5

857

858

CH3

Cl

CH2Cl2
-20 oC

CH + (C6H5)3P + CH3CN
OH

CHCH3
(92%)

+ Ph3PO + CHCl2CN
(S)-2- 95%-
.
- 1325
:
CH3

CH3

+ (C6H5)3P + CCl4
CH2OH

CCl4
50 oC

CH3

CH3

CH2Cl
(100%)

CH3OH

CH2Cl2
0-15 oC

C C CH3 + (C6H5)3P + CCl3 C CCl3

CH2

H
CH3
CH2

CH3

C CH CH3

(92%)

ClCH2

C CHCH3
(2%)

Cl

CH2OH
CH3CN
+ (C6H5)3P + CCl3COOC2H5 0...(-10) oC
H

CH3
H
CH3

CH2Cl

CH3 CH CH CH2

Cl

(98%)

(0,5%)

.
(5)3.12

N-- N,
:

858

859

CH2Br

CH2OH
O

1) (C6H5)3P-NBS, , 50
2) (H3CO)2O

OH
OH

O
OAc

OAc

OCH3
(66%) OAc

OCH3
OH

,

(),
[(3)2N]3.
:
-C5H11CH-C

CH + [(CH3)3N]3P + CCl4

,
25 oC

OH
-C5H11CH-C

Cl
CH3
C6H5

CH + [(CH3)3N]3P=O + CHCl3

(62%)

1) [(CH3)2N]3P, CCl4, , -30 oC

C6H5
2) N(C4H9)4I

C CH2OH

CH3
C CH2I
CH3

CH3

(70%)

, , .

, n- (),
-:
O
ROH + n-CH3C6H4-S-Cl
O

0 oC

n-CH3C6H4S-OR + C5H5NH Cl
O

n- -
, ,
-.
ROSOCl ROPBr2
859

860

.
,
:

CH3CH2CHCH2CH3 + NaBr
OTs

CH3

CH3
CH3

Br (85%)

1) CH3SO2Cl; ; C5H5N
2) LiCl; ; 0-20 oC

OH

CH3CH2CHCH2CH3

25 oC

CH3

CH3

(100%)

Cl

CH3

NaI

Cl(CH2)5OTs ; 0-20 Cl(CH2)5I + NaOTs

82%

,
, .
,
:
RCHCH=CH2

1) CH3SO2Cl; C5H5N
2) LiCl; ; 0-20 oC

OH
RCHCH=CH2 + RCH=CH-CH2Cl
Cl
R = CH3
R = (CH3)3C

(73%)
( 6%)

(27%)
(94%)

.

, -

.

.

860

861

-,
:
C6H5CH2Br + KF

CH3(CH2)6CH2Br + KF

KF + -C6H13CHOTs
CH3
KCl + -C8H17OTs

NaCl + -C10H21Br

18--6

20 oC

C6H5CH2F + KBr
(100%)

18--6

C16H33P(C4H9)3Br
2-

18--6

(C8H17)3NCH3Cl
2-CH2Cl2

CH3(CH2)6CH2F + KBr
(92%)

-C6H13CH-F + KOTs
(57%)

CH3

-C8H17Cl + KOTs
(89%)

-C10H21Cl + NaBr
(86%)

11.1.3..

.
,
- .

.
.
:
R1CH2CH R2

H ,

R1CH2CH R2

-H2O,

OH2

OH
R1CH2CH R2

-H ,

+H2O

R1CH=CH R2 + H

1 (. 10). 1-

861

862

, ..
.
E1
.
85%- 160-170 60-70%-
90-100 ,
:
CH3CH2CH2CHCH3

62% H2SO4
90-95 oC

CH3CH2CH2CH=CHCH3 +
(80%)

OH
+ CH3CH2CH2CH=CH2 + H2O
(20%)

CH3

85% H3PO4
160-170 oC

CH3 + H2O

CH3 +
(79-84%)

OH

20-50%-
85-100 :
CH3
CH3CH2

C CH3

45% H2SO4
90 oC

CH3
CH3CH C CH3 + CH3CH2 C CH2
(80%)

OH

(20%)

CH3

,
,
:
(CH3)2C

(CH2)3CH2OH

40% H2SO4
90 oC

(CH3)2CH=CH(CH2)2CH2OH

OH
,
1,2- -.

.
: > >
1-
:

862

863

CH3
CH3

CH CH3

CH3 H

85% H3PO4
80 oC

CH3

CH3 OH

C CH3

CH3 OH2
CH3

CH3
CH3

CH3

CH CH3

CH CH3

-H

CH3

CH3

(CH3)2C=C(CH3)2 + CH2=C-CH(CH3)2
(80%)

OH
(CH3)2CHCH2-C-CH3
1,2-

CH3 (20%)
H

H2SO4
80 oC

(CH3)2CHCH-CHCH3

(CH3)2CH-CH-CH2CH3

(CH3)2C=CH-CH2CH3 + H

, ,
.

. -1
96%- 170-190 ",
:
CH3CH2CH2OH

96% H2SO4
180 oC

CH3CH=CH2

. 2- , , , :
O
RCH2CH2-O-S-OH + H2O
O

RCH2CH2OH + H2SO4

R-CH-CH2-O O
S
H
HO O

H2SO4
170-190 oC

RCH=CH2 + H2SO4 + HSO4

863

864

, 2,
, - -:
RCH2CH2OH + H2SO4
HSO4

RCH2CH2OH2 HSO4
E2

+ RCH2CH2OH2

RCH=CH2 + H2SO4 + H2O

96%- 130 -140
.

, ,
SN2- :
2CH3CH2OH

96% H2SO4
135oC

CH3CH2OCH2CH3
H

CH3CH2OH + CH2OSO3H

CH3CH2OCH2CH3 + HSO4

CH3
CH3CH2OCH2CH3 + H2SO4

H
CH3CH2OH + CH3CH3OH2

CH3CH2OCH2CH3 + H2O

CH3CH2OCH2CH3 + H3O
- ,
,
.
:
HOCH2CH2OH + HOCH2CH2OH

H2SO4
130-140 oC

O + 2H2O

(50-55%)

HO(CH2)4OH

H3PO4 260-280 oC
90-100

864

O (99%)

865

,
,
ROR, R'OR'
ROR'.
- ,
,
.
,
350-450 :
H3CH2OH

Al2O3
360 oC
Al2O3

CH2=CH2 + H2O
(98%)

OH 400-450 oC

+ H2O
(90%)

(CH3)2C(OH)-C(OH)(CH3)2

Al2O3
420-470 oC

CH2=C(CH3)-C(CH3)=CH2 + 2H2O
(70-85%)

-
,
. , , -1
-2
-3, -1.

.

- .

11.1.3..

. . 1852
:

865

866

R1ONa + R2X

R1O R2 + NaX

X = Cl; Br; I; OTs; OTf; OSO2R

,
:
(CH3)3CCH2ONa + C6H5CH2Cl

65 oC

(CH3)3CCH2OCH2C6H5 + NaCl
(68%)

OK

+ CH3(CH2)15CH2OTs 40 oC

OCH2(CH2)15CH3
+ KOTs

(85%)

OK + CH3(CH2)3Br

O(CH2)3CH3 + KBr

65 oC

(80%)

NO2
(CH3)2CHONa + CH3CH2Br

NO2

40 oC

(CH3)2CH-O-CH2CH3 + NaBr
(85%)

SN2 - -.
, .
,
, ,
E2:
(H3)3COK + CH3I
CH3ONa + (CH3)3CCl

(CH3)3C-O-CH3 + KI
(CH3)2C=CH2 + NaCl + CH3OH

,

, - .

866

867

11.1.3..

:
[O]

RCH2OH

R-C

[O]

R1CHR2

[O]

R-C
OH

R1 C

O
R2

,

.


- (VI), (VII) (IV).


.

,
.

r3 : CrO3.2C5H5N (
-) rO3l-55N+ ( )
. CrO3.2C5H5N
(VI) 10-15 .
r3
20%- . CH2CI2 l3:
C5H5N + CrO3 + HCl

10 oC
H2O

867

C5H5NH . CrO3Cl

868

,
,

.
,-
(IV)
n2 (. 11.3). .
(IV),
.


,
.
11.3
(VI) r3

2C5H5N,

(IV)

1)
CrO 3. 2C5H 5N
CH 3(CH 2)5CHO (93%)
CH 2Cl2; 25 oC 10

CH 3(CH 2)5CH 2OH

2)

C5H 5N . CrO 3. H Cl
CH 2Cl2; 25 oC

CH 3(CH 2)5CH 2OH

CH 3(CH 2)5CHO

(78%)

3)
O 2N

CH 2OH

CrO 3. 2C5H 5N
CH 2Cl2; 20 oC

CHO (97%)

O 2N

4)
CH 3
CH 3

CH 3

C5H 5N . CrO 3. H Cl

OH

CH 2Cl2; 25 oC

CH 3

CH 3
CHO

CH 3

5)

868

(97%)

869

C5H 5N . CrO 3. H Cl

OHC-(CH 2)4-CHO (68%)

HOCH 2(CH 2)4CH 2OH CH Cl ; 25 oC

2 2
6)
CH 3(CH 2)4C

CCH 2OH

C5H 5N . CrO 3. HCl

CH 2Cl2; 25 oC

CH 3(CH 2)4C

C-CHO (84%)

7)
(CH 2)6-CH 2OH

CH 3CH 2CH(CH 2)4

CH 3

C5H 5N . CrO 3. H Cl

CH 2Cl2; 25 oC 2

(CH 2)6-CHO

CH 3CH 2CH(CH 2)4

CH 3

(80%)

14--8 Z - -

8)
H

CH 3(CH 2)3

(CH 2)3-CH 2OH

H
H

C5H 5N . CrO 3. H Cl
CH 2Cl2; 25 oC

H
H

CH 3(CH 2)3

(CH 2)3-CHO

H
H

(82%)

5Z,-7 - -

9)
CH 2OH

CH 3CH 2
H

CH 3CH 2

MnO 2

CHO
(64%)

2l2
, 20 oC

10)
CH 2 CH CH C CH
OH

MnO 2

CH 2 CH CH C CH (70%)

CH 2Cl2; 20 oC

11)

869

870

CH 3(CH 2)2C

C C

MnO 2

C CH CH CH 2OH

CH 2Cl2; 25 oC

C C C CH CH CHO (90%)

CH 3(CH 2)2C
12)
CH 3

CH 3

CH 3

CH 2OH

CH 3

CH 3

CH 3

CHO

MnO 2
, 0 oC

CH 3

CH 3

CH 3

(80%)

CH 3

13)
CH 3

HOCH 2

CH 3

OHC
MnO 2

CH 3

(62%)

CH 3

, 20 oC

CH= C(CH 3)2

CH= C(CH 3)2

,
:
CH3(CH2)5

H CH3

CrO3.2C5H5N

CH3(CH2)5

CH2Cl2; 25 oC

OH
(CH 3)3C

OH

C5H 5N . CrO 3. H Cl
CH 2Cl2; 25 oC

O (98%)

(CH 3)3C
CH 3 O

CH 3 OH
CH 3

CH3 (97%)

CH 3

C5H 5N . CrO 3. H Cl
CH 2Cl2; 25 oC

(82%)

( )

4--3,17-

, ,
-
r3 . ,
, 0-25 o.
,
870

871

, : ,
(III), , .
,
, ,
:
(CH 3)3C

OH

CrO 3-H 2O-H 2SO 4

; 20 oC

OH
CrO 3-H 2O-H 2SO 4

(95%)

; 20 oC

OH

O (90%)

(CH 3)3C

CrO 3-H 2O-H 2SO 4

; 20 oC

CH 3CH CH CH C CH

CrO 3-H 2O-H 2SO 4

; 20 oC

(88%)

CH 3CH CH CH C CH
O

OH
C 6H 5CH C CH

CrO 3-H 2O-H 2SO 4

; 20 oC

OH

C 6H 5C C CH

(75%)

(80%)

.
, , ,
:
CH3(CH2)8CH2OH
CH2OH

CrO3-H2O-H2SO4
; 20 oC

CH3(CH2)8COOH (93%)
COOH

CrO3-H2O-H2SO4
; 20 oC

(85%)

C6H5
HO CH2 C

C CH2 OH

C6H5
CrO3-H2O-H2SO4
; 0 oC

HOOC

C C COOH (58%)

. .
r3 .

871

872

, -
, ,
Cr(IV). 3D(H)3
-2
kH/kD=7.
, ,
. ,
(III),
:
R2CH-O-Cr VI O3H

(1) R2CHOH + CrO3

O
VI

(2) R2C-O-Cr
B:

OH

IV

C O + BH + HO-Cr
R

O
O

B: = H2O, HSO4 , C5H5N

, , (IV),
, , , -,
:
2R2CHOH + 2Cr(IV)

2R2COH + 2Cr(III)

R2COH + Cr(VI)

R2C=O + Cr(V)

R2CHOH + Cr(V)

R2C=O + Cr(III)

2Cr(V)

Cr(IV) + Cr(VI)

,

.
Cr(IV) ,
Mn(II) Ce(III), Cr(IV).
Ce(IV) , Ce(IV)
Cr(IV) Cr(III) Cr(VI):

3Cr(IV)

Ce(IV)

2Cr(III) + Cr(VI

872

873

,
, :
O
(CH3)3C-O-Cr-OH
O

(CH3)3COH + CrO3

O
(CH3)3COH + (CH3)3C-O-Cr-OH
O

O
(CH3)3C-O-Cr-O-C(CH3)3
O

-
.
,
3r3,

:
O O
CH3C-O-Cr-OH
O

CH3COOH + CrO3

CrO3

C6H5 CH C(CH3)3

C6H5

CH3COOH

OH

C C(CH3)3
O

(64%)

.
1,1-,
. 3-
:
OH
RCHO + HOH

RCH
OH

OH
C

O
OH
RC O Cr OH
O
H

+ CrO3

OH

873

874

OH

B:

O
R C O Cr OH
O
H

E2

O
+ HO Cr

RC
OH

+ BH
O

, ,

.
,
.

.

, - .

.
-
:
O
HOCH2

Ag2CO3/o

CH=CH2

H C

CH=CH2

; 80 oC

(80%)

.
:
ClCH2CH2CH2OH

70%- HNO3
25 oC

O
ClCH2CH2C

(78%)

OH

,
.
50%-
:
OH

50%- HNO3; V2O5

55-60 oC

874

HOOC(CH2)4COOH
60%

875

- .
, ,
10-30 120-150
.

(CH3)2S O + RCH2OTs

150 oC

R-C-O-S(CH3)2

OTs

H
HCO3

NaHCO3

(CH3)2S + RCHO + H2O + CO2 + TsONa

60-70%

,
SN2
.
- ,
-
. -
2 ,
. .
CH3(CH2)5CH2OTs
Br

CH2OTs

NaHCO3
150 oC, 5
NaHCO3
120 oC

CH3(CH2)5CHO + (CH3)2S
70%

Br

CHO + (CH3)2S
65%

,
150 -180
.

, .
,
.

875

876

,
0 .
,
, N- N,N-
C6H11N=C=NC6H11.
,
-
,
-
.

SO3,
.
O
C5H5N-S-O

+ O-S

C5H5N +

CH3

O
O
R2CHOH +

CH3

O-S-O-S(CH3)2

O
0 oC

R2C-O-S(CH3)2 + HSO4

O
R2C-O-S(CH3)2

H
0 oC

O-S-O-S(CH3)2

R2C=O + C5H5NH.HSO4 + (CH3)2S

H
C5H5N:
SO3 ,
N,N- ().
N,N ( -).
N

C N

+ O-S(CH3)2

NH C N
O S(CH3)2

876

877

H
R2C-OH +

NH C NH

NH C N

O S(CH3)2
+ R2C-O-S(CH3)2

R C R + (CH3)2S + H

N-
, -30
:
O

O
(CH3)2S

N Cl

, 0 oC

S(CH3)2Cl

R2CHOH
-30 oC

O
R2C O

S(CH3)2Cl

N(C2H5)3
0-...-30 oC

R2CO + (C2H5)3NH Cl

:
CH3(CH2)6CH2OH

,
C5H5NHOCOCF3 -20 oC

CH3(CH2)6CHO
(100)%

CH3 O

CH3 OH
CH3

CH3

, 0 oC
C5H5NH OAc

(93%)

CH3 C8H17

CH3 C8H17
CH3

CH3

, -SO3
C5H5N; CH2Cl2

HO

(83%)

O
H

(1937).

877

878

, -.

( -). ,
- -,
, , (2,3,5,6--1,4-):
R3

R1
CH OH +
R2

C O

Al[O-C(CH3)3]3

R4

R1
C O
CH OH +
4
2
R
R
R3

R1

R1
(CH3)3COH +

CH OH + Al[OC(CH3)3]3
R2

R3

R1
R2

R2

C O Al[OC(CH3)3]3

C O Al[OC(CH3)3]3

C O
R4

H
R1
R2

C
H
R3

O
C

Al[OC(CH3)3]3
O
R4
R3

R1
C O
R2

R4

C O Al[OC(CH3)3]3
H

-
,


.

878

879

:
CH3
CH3 CH-(CH2)3CH(CH3)2
CH3

, 80 o, 8

Al[OC(CH3)3]3

CH3

HO

CH3 CH-(CH2)3CH(CH3)2
CH3
(63-70%)

O

.
,
- .
, ,
:
CH3CH2CH2CH2OH

OH

CuO-Cr2O3
, t

CH3CH2CH2C
(62%)

O
H

+ H2

Cu, 600 oC

+ H2
(92%)

CH3OH

Cu Ag
600 oC

HC
(88%)

+ H2

11.1.3..

879

880

,
. , ,
r(2)n
. : 1) , 2)
3)
.

-
2,3-:
H

ROH +

RO

(90-100%

2-

2,3-

, ()
,
(RMgX, RLi, NaH, NaNH2, RONa .),
. -
,
:
HCl CH3OH
20 oC

RO

+ ROH
HO

-:

HO

Br

1) CH3COCH3

MgBr 2)
HO
HCl CH3OH

880

Mg

Br
OH
C CH3
CH3

881

,
(CH3)3SiCl.
-:
N(C2H5)3

ROH + (CH3)3SiCl

KF

ROSi(CH3)3

ROK + (CH3)3SiF

, .
. ,
[(3)3](3)2Sil KF (C4H9)4NF.
- ()

() .
,
r
.
:
RONa + C6H5CH2Br
ROH + (C6H5)3CCl

ROCH2C6H5

C5H5N
CHCl3

ROC(C6H5)3

H2/Pt

HBr
CH3COOH

ROH + C6H5CH3
ROH + (C6H5)3CBr

(., 1976):
RONa + ICH2SCH3

ROCH2SCH3 + NaI

, , ,
20 o (II)
-.

.

881

882

11.2.
, , .

, ,
-, :
OH

CH 3 CH CH 2OH
OH
1,2-

OH
-1,2-

CH 3 CH CH CH CH 2CH 2OH

OH

OH

CH 3 CH 3 OH

CH CH 2CH 2CHCH 3

4,5--1,3-
1--1,4-

, 1,2-, 1,3-, 1,4- .

1,2- , -
() . , ,
(. 5), :
CH 2 CH 2

CH 3 CH CH 2OH
OH

OH OH

(1,2-)

(1,2-)

,
- ,
.
,
.
- , -
,
:

882

883

OH
R2
C

R1

R1

O
R2

OH

+ H2O

,

(. 16; . 3).

11.2.1.

1,2-
- -
, . 5 (. 3).
1,2-
.
- , ,
- , ,
. 1,2- .
, . -
1,2-,
:
2R

R
+ Mg

C O Mg

(-)

R 2C O M g

R 2C
O

Mg

CR 2
O

H 2O

R
R

OH

OH

, ,
,

883

884

1) Mg,
CH3CCH3 2) H O
2

R
R

OH

OH

R (43-50%)

(, )
40-50%.

,
,
.
TiCl4 (., 1976).
e :
Zn, TiCl4
, 25 , 2

C 6H 5COCH 3

-C 7H 5C

O
H

Mg(H g), TiCl4

, 0 , 13

C 6H 5
CH 3

C 6H 5
C

OH

OH

(91%)

CH 3

-C 7H 15 CH CH C 7H 15-

(80%)

OH OH
OH

Mg(H g), TiCl4

2 CH 3C(CH 2)2CCH 3 , 0 , 2,5

O
O

CH 3
CH 3

(81%)

OH

.

1,3- 1,4-:
C 6H 5

CH 3
C 6H 5

O CH 3 O

C 6H 5

CH 3OH , pH = 3,7

HO
CH 3

C 6H 5
OH
CH 3

, .

884

885

(III) il3
- .
,
,
, :
2

TiCl3, Li

+ TiO2

(79%)

TiCl3, K

2 CH 3(CH 2)3CHO

CH 3(CH 2)3CH= CH(CH 2)3CH 3 + TiO2

77%, -: -=3:7

, (II)
-
iO2:

R2

O
C

R1

Ti
O
C

R2

R4

R1

R3

R4
C

R3

+ TiO 2

-1,2-

. 1,2-:
OSi(CH 3)3

O
1) LiN(Pr- i)2; ; -78 o C
2) (CH 3)3SiCl; ; -78 o C

OH
OH
1) B2H 6,
2) NaOH-H 2O 2; CH 3ONa; CH 3OH

(81%)

1,3-
(. 17) :

885

886

R 1CH CH 2 C

OH

N aBH 4

R 1 CH CH 2 CH

R2

OH

R2

OH

. 1,3 -
1,3-:
1) 2Hg(OAc) 2; -H 2O

RCH= CH-CH= CH 2

2) NaBH 4; NaOH

RCH-CH 2-CH-CH 3
OH

OH

. (2)
(4):
CH 3CH= CH-CH= CH 2

1) 2Hg(OAc) 2; -H 2O
2) NaBH 4; NaOH

CH 3CH-CH 2-CH-CH 3
OH

OH

(79%)

1,3- .
(1917).
1,3-
- 1,3-:
O

CH 3
C

CH 2

25%- H 2SO 4

HC

HOH; 80 o C

CH 3
CH 3
O
CH 3

CH 3
C
CH 3

CH 2CH 2OH
OH

1,3- 1,3- .
1,3-.

1,3-, 1,3-
886

887

.
1,3-,
1,3-.
.

2,6-:
LiAlH 4

C 2H 5OOC-(CH 2)8-COOC 2H 5
CH 3CO(CH 2)3COCH 3

LiAlH 4

HO-(CH 2)10-OH (75%)

CH 3CH(CH 2)3CHCH 3 (80%)

OH

OH

11.2.2.

, .
1,2- ,
.
.

11.2.2..

,
,
,
.
,
. 1,2-
: 1) ;
2) , , -
; 3)
. ,

887

888

, ..
.
,
. 1,2-
1,3- 48%-
:
(CH 3)2C

C(CH 3)2

OH

25%- HBr, t

CH 2

C CH 2 (62%)

CH 3 CH 3

OH

450-470 o:
(CH 3)2C

Al2O3

C(CH 3)2

450-470 o C

CH 2 C

C CH 2 (70-85%)

CH 3 CH 3

OH OH

, 1,2-, , n, (F3 .), 1,2 , -.

.
. 1859 .
,

:.
CH 3 CH 3
C

CH 3 C

CH 3

H 2SO4

CH 3
CH 3 C

CH 3 + H 2O

CH 3 O

OH OH

1,2 . 11.4.
11.4
1,2-

(C 6H 5)2C

CHC 6H 5

96% H 2SO4
0 oC

OH OH

888

(C 6H 5)2C

C C 6H 5 (100%)
O

889

(CH 3)2C

15% H 2SO4

CH 2OH

(CH 3)2CHC

OH
CH 3CH

35% H 2SO4
t

CHCH 3

CH 3

(100%)

C CH 2CH 3 (81%)
O

OH OH
O

OH
CH 2CH 3

BF 3. (C2H 5)2O

CCH 2CH 3

CH Cl3

OH
CH 2CH 3

(100%)

CH 2CH 3

OH
H 2SO4

(100%)

0 oC

OH

1,2-, ,
. . 11.4

.


:
O
O

Mg(H g), TiCl4

OH

OH

H 2SO4
0 oC

10 4

7
6

5
9

[4,5]--6

.
1,2 , 1,2-

.
:

889

890

R1 R1

R1 R1
R C

C R

R C

R1
-H 2O

R C

OH OH 2

OH OH

OH

R
R1

R1

R1
R C

-H

R C
O

OH 2 R 1

C R + H
R1

,
,
2, , .
,
:
*
C 4H 9-
CH 3 C

*
C 4H 9-

40% H 2SO4

C(H 3)2

CH 3 C

OH OH

(S)-

C(CH 3)2

(66%)

(S)-

1,2-
. , -,

.

. ,
1,2-
:
R1 R1

R1 R1
R C

R C

OH OH 2

OH OH

R1

R1
R C
OH 2

R1

R C

890

R1 + H

C
R

891

1,2-
,
:
(C 6H 5)2C

H 2SO4
0 oC

C(C 6H 5)2

OH OH
H 2SO4
t

(C 6H 5)3C

(C 6H 5)2C

C(C 6H 5)2
O

C C 6H 5
O

C 10H 7-
C 6H 5CH

25% H 2SO4

CC 6H 5

C 6H 5CH

OH OH
H 2SO4

C
O

C 6H 5

C CH
O

C 10H 7-
C 6H 5

C 10H 7-
C 6H 5

,
1,2- .

. 26 (. 4).
- 1,2-
R-()-2 85%-
- 1,4- .
1,4- 1,5-
:
CH2
CH2

HO

OH
+
OH

HO

CH2 H SO CH2
2
4
CH2

140 oC

CH2

CH2
CH2

1,4- (50-55%)

891

892

CH2
85% H3PO4 , 260-280 oC, 90
Ca3(PO4)2 , 320 oC

CH2CH2CH2CH2
OH

OH
H2O

SN2

CH2
OH

CH2
CH2

O
H

CH2
CH2OH2

CH2
O

CH2

+ H3O

(98-99%)

HO(CH 2)5OH

57% H 2SO4

O (100%)
CH 2

CH 2OH
85% H 3PO 4
t

O
CH 2

CH 2OH

(90-94%)

1,2-,
1,3-
,-.

,
:
CH3

C5H5N
0 oC

TsOCH2CH2CH2CCH2CH3
CH3

C 6H 5 CH
OH

CH C CH

O
(92%)

1) TsCl, C5H 5N , 0 oC
2) N aOH -, 20 oC

OH

CH2CH3
CH3

H
C 6H 5

H
O

CH

(80%)

11.2.2.. 1,2-

5
.
- -

892

893

1,2-
.
1,2-
H5IO6 (., 1928 .),
b(3)4 (., 1931 .):
CH 3(CH 2)7CH CH(CH 2)7COOH

K MnO4
H 2O 40 o C

CH 3(CH 2)7CH(OH)CH(OH)(CH 2)7COOH

-

H 5IO6
-

CH 3(CH 2)7CHO + OHC(CH 2)7COOH + HIO 3

(76%)

OH
Pb(OCOCH 3)4

+ Pb(OCOCH 3)2 + CH 3COOH

CH 3COOH

O (82%)

OH

b3O4
:
Pb 3O4 + (CH 3CO)2O

CH 3COOH
55 o C

Pb(OCOCH 3)4
(70-75%)

, 1,2-
. 1,2-,
- , - ,
5IO6 , .
1,2-
.
-
-
:

893

894

R1
H

R2

OH

OH

R1
+ HIO 4

R2

O I O
HO OH
R 1C

+ R2 C

H
R1
R2

O
O

OH

OH

R4

C
R2

R3

C
R2 O

+ Pb(OCOCH 3)4

C
O

R4

Pb
CH 3OCO

R1

+ H 2O

R1

R3
C

O
H

R3
+

C
R4

OCOCH 3

Pb(OCOCH 3)2 + 2CH 3COOH

- -,
-
-. , ,
. 1,2-,
-
. , , -9,10 -1,6,
- 300 , -,
:
O

OH
Pb(OCOCH 3)4

Pb(OCOCH 3)4

CH 3COOH

CH 3COOH

OH

894

OH
HO

895

R1
R1 R2 C

Pb(OCOCH3)4

C R3 R4

R2
O

H O C

OH OH

R3

R1 C R2 + R3 C R4

Pb(OCOCH3)2
OCOCH3

R4

+ Pb(OCOCH3)2 + CH3COOH

5 (. 1)
. ,
KMnO4NaIO4 OsO4NaIO4.
(VIII) -1,2-,

n (VII) Os (VIII).
1,2-
.
(IV), (V),
C6H5I(OCOCH3)2.
NiO2 (IV):
H
C 6H 5C

H
CC 6H 5

OH OH

N iO2
, 50

2C 6H 5CHO (85%)

OH
MnO2
CH 2Cl2 20 o C

O (90%)

OH

1,2- (. 10).
1,3---
2 :

895

896

H
R
C OH
R

C OH

C N

H
C O

(R1O)3P

H
R
R

H
C

O
H

+ (R1O)3P=S

O2 +

H
C 6H 5C

1)
H
CC 6H 5

C N
S

2) P(OC 4H 9)3

OH OH

C 6H 5

H
C 6H 5

H
(92%)

11.3.

11.3.1.

,
, , :
(H3)2CH-OC2H5

(CH3)2CH-O-CH(CH3)2

CH3-O-H2CH2CH2CH3
-

.
:
CH 2CH 3
CH 3CH 2CH 2O CHCH 2CH 2CH 3

H3OCH2CH2OCH3

3-

1,2-

896

897

CH 3
CH 3

C CH 2CH 2CH 2 O CH 2CH 3

CH 3
1--4,4-

, 2. --
112 33,
sp3- .

( .),

,
.

11.3.2.

:
,
..

11.3.2..

.
:
BrCH 2CH 2OH

H 2SO4
130 o C

BrCH 2CH 2OCH 2CH 2Br + H 2O

(72%)

.
, ,
, - :

897

898

(CH 3)3C

OH + CH 3CH 2CH 2CH 2OH

(CH 3)3C O

KHSO 4
100 o C

(CH 2)3CH 3 + H 2O

.
, .

.

11.3.2..

(. 5, . 1), ,
,
. ,

, :
1) Hg(OAc) 2;

CH 3(CH 2)5 CH CH 2 2)NaBH 4;

CH 3(CH 2)5CHOCH 2CH 3

CH 3

(92%)

.
:
CH3
1) (F3COO)2Hg; (CH3)3COH
2) NaBH4

O CH CH3
(98%)

1) (F 3COO) 2Hg; (CH 3)2CHOH

C 6H 5CH= CH 2 2) NaBH 4

C 6H 5CHOC(CH 3)2
CH 3

(93%)

(. 5, . 1).

898

899

11.3.2.. .
:
RX + R1OM

ROR1 + MX

, .
.

, -11. -
,
. -
,
, .. -
. ,
.
O

O
O

O
O

O
O

O
O

12--4

15--5

18--6

24--8

- -18-- .
1967 .
-(2-) :
ONa

ClCH2CH2OCH2CH2Cl
+

ONa
C4H9OH-H2O; 100 oC

NaO
+

ClCH2CH2OCH2CH2Cl

NaO

O-CH2CH2-O-CH2CH2-O
(45%)

O-CH2CH2-O-CH2CH2-O
-
.

899

900

18--6 (.) 24--8-. -

:
OH

Cl

OH

KOH

(40-60%)

H2O-

Cl

18--6

OH
O

TsO
+

O
O

OH

(CH3)3COK

(15%)

TsO

24--8

18--6-
, 12--4 - .
- ,
. ,
,
.
.
+ ,
18---
.
,
:
OTs
OH
O

TsO
O (CH ) COK O
3 3

O
OH

11

O
TsO

O
O

O
O

Crown (.) - .
900

O
OTs

K
O
O

901

,
, .
-
.
,
. 1,20
12--4-

1,21,5 ; (d = 1,9 )
15--5 (d = 1,7-2,2 ), (d = 2,66 ) - 18--6 (d

= 2,6-3,2 ). d = 3,38 24--8 4 .

-, ,
- - -

:

[2,2,2]

11.3.3.

, .
,
,
.

(. 19, . 3),
.
.
, , -, ,
, ,
901

902

RMgX,
, , -
.
- BF3, lr3, lR3, SbCl5, SbF5, SnCl4, ZnCl2 .. 1:1
1:2:
(C2H5)2O + BF3

(C2H5)2O

BF3

CH2CH2
CH3O
OCH3

CH3OCH2CH2OCH3 + ZnCl2

Cl

Zn 2
Cl

,
, - .

I-I...+OR2.
. ,
,
.
().
:
R 2 O + R 1F

SbF5

O-R1

SbF5

.
1937-1940 .
:
3CH2

CH CH2Cl + 4(C2H5)2O

BF3 + 2(C2H5)2O

O
, 36 oC

3(C2H5)3OBF4 + (ClCH2CH-O-)3B
90%

CH2OC2H5

902

903

- ,
:
R2O + CF3SO3R

CHCl3

R2O + FSO 3H

R3OSO3CF3
R3OOSO2F

RC N: + (C2H5)3OBF4

RC N-C2H5BF4

CH2Cl2

ROH + (C2H5)3OBF4

R2S

ROC2H5

O + (C2H5)3OBF4
R1
C
O M

R2S-OC2H5BF4

R2 (C2H5)3OBF4

R2
R1

OC2H5 R3

R3

, .

11.3.3.

120-150
(48%) r HI.
1861 . .. 2 48%- .
, :
CH3 CH COOH + HI

140 oC

CH3CH2I + CH3 CH COOH

OH

OC2H5
C6H5OCH3 + HBr

150 oC

C6H5OH + CH3Br

, ,
:

903

904

H2O
10 oC

C6H11OC(CH3)3 + HBr

C6H11OH + (CH3)3C-Br

. ,
, SN2- SN1-.
, SN2-,
- -
:
I +

R1

SN2

R2

R1I + R2OH

H
, ,
, ,
()
. - -

,
SN2-.
, ,
, SNl-
. ,
HI r
:
OC(CH3)3

CH3COOH
0 oC

OH + (CH3)2C=CH2
90%

HI r .
l3
r3. -20 o.
, :

904

905

CH3CH2CH2OC6H5

1) BCl3; CH2Cl2;
-10 o
2) NaOH; H2O

C6H5OH + CH3CH2CH2Cl
(75%)

1) BBr3; ; 0-20 o
2) NaOH; H2O

CH3(CH2)3-O-(CH2)3CH3

CH3(CH2)3Br + CH3(CH2)2CH2OH
(77%)

11.3.3..

,
,
-
.

CH3 CH O

2p- 2p-
.
CH3CH2OCH2CH3 + Cl2

h
-20 oC

CH3CH-O-CH2CH3 + HCl
Cl

CH3CH-O-CH2CH3 + Cl2

h
-20 oC

Cl

CH3-CH-O-CH-CH3 + HCl
Cl

Cl

-
. 103-106
:
CH3OCH2Cl + KCN

CH3OCH2CN + KCl

. ,
, .
,

905

906

.
,
, , .

:
X + RCH2-OCH2R

RCH-OCH2R

:
RCH-OCH2R + O-O

RCH-OCH2R
O O

RCH-OCH2R + RCH2OCH2R
O O
RCH-OCH2R + RCH-OCH2R ..
O OH

- (II)
(II).

11.3.4. ()

( )
, .
,
,
.
, ,
,
.

906

907

11.3.4..

. 5
(. 1).
.
5. .

:
CH3

H
+

C C

CO3H

COOC2H5

ClCH2CH2Cl

CH3

H
C C
H O COOC2H5

CH 3(CH 2)5CH= CH 2 +

CO3H

(70%)

C6H 6; 25 oC

CH 3(CH 2)5CH CH 2
(81%)

Cl
+

CH 2Cl2

CO3H

O (78%)

Cl
OH
B:

O
X

,
, -
, - .
N- N-
-
. ,
, - 2- . .

907

908

SN2- , -
, -:
H
OH

Cl

N aOH

OH
H

H 2O

H
Cl

SN2

H
(73%)

Cl

- -,
:
H

Br

Br

K MnO4
H 2O, 0-5 oC

HO
H

OH
H

Br

Br

K OH
CH 3OH

- -
:
CH 2= CH 2 + O2

Ag/Al2O3
250-330 oC

CH 2

CH 2
O

(75%)

11.3.4..

: - -, ,
, -, .

SN2- .

908

909

- - 2-.
1,2- . 5 (. 1).
)

HO

OH , S N 2

H 2O

H O
H

HO
OH

H 2O
)

H 2O

O H
H

OH

OH

OH

(70%; )

,
.

, :
O
CH 2 CH CH CH 3
CH 3

O
CH 3CH 2ON a
CH 3CH 2OH

CH 3

CH 2 CH CH CH 3
OCH 2CH 3

CH 3
H 3O

CH 2CH(OH)CHCH 3
OCH 2CH 3

CH 3ON a

C 6H 5 CH CH 2OCH 3

CH 3OH

C 6H 5

OH

(85%)

.
-
. ,
, -.

909

910

SN2-:
H
O
CH2 CH2

O
CH2 CH2

+H

:X

HO-CH2CH2-X

SN2 SNl.
,
SNl-:
H
R
R

O
C CH2

R
C
R

CH2OH

O
C CH2

CH3OH

R
C CH2OH + H
R
OCH3

SNl-
, SN2-.
SNl-,
. SN2- SNl-


.

e

.
-
,
:

910

911

R1
CH 2 + R 2M rBr

C
H

R1

BrM gO

O
H 2O

CH CH 2 R 2

R 1CH CH 2 R 2

N H 4Cl

OH

,
. ,
:
CH3(CH2)3CH

1) (CH3)2CuLi;

CH2

2) H2O

CH3(CH2)3CH

CH2CH3

OH

(98%)

,
SN2-,

:

CH3

1) LiAlH4; ; 0 oC
2) H2O

O
CH3

CH3
HO

O H
CH3

CH3CH2

(83%)

1) LiAlH4; ; 0 oC
2) H2O 0 oC

HO
CH3
CH3CH2

H
CH3 (74%)
D

:
CH3
CH3CH2

O H

1) BH3;
2) H2O

CH3

(CH3)2H-CH-CH3
OH

.
,
.

911

912

:
CH

CH2

(CH2)8COOC2H5 + H2

Pd/C
, 1

CH3CH-(CH2)8COOC2H5
OH

(80%)

,
:
CH2

CH

(CH2)7CH3 + H2

Ni

HO(CH2)9CH3 (85%)

150 , 70

.
- Z-
( )
, .

. -
-
,
:
R1

R4

(6H5)3P
SN2

R2

R3
R1
R2

R1
R2

R4
3
P(C6H5)3 R
R1

R3

R4
P(C6H5)3 O

R3

+ (6H5)3P=O
R2

R4

.
:

912

913

R4

R1

-ClC6H4CO3H

R3

R2

R1

R4

R3

R2
R3

R1
(C6H5)3P
t

R4

R2

-
, ,
, - .
- :
O
CH2 + HOH

CH2

1%- H2SO4
H2O; 70 o

HOCH2CH2OH
(90%)

,
- :
O
CH2

CH2 + HOCH2CH2OH

HOCH2CH2-O-CH2CH2OH

:
O
HO

+ CH2

HOCH2CH2O

CH2

O
CH2

CH2

HOCH2CH2-O-CH2CH2O

n CH2 CH2

HO-(CH2CH2O)n+2H

, . ,
, ,
, , .

913

914

,
.
()
. ()
:
O
CH3ONa + CH2

CH2

CH3OH

CH3OCH2CH2OH ()

, ,
(, ),
(),
().
-

,
.
-, -
:
(CH3O)2SO2 + HO-CH2CH2-O-CH2CH2OCH3
NaOH
H2O

CH3OCH2CH2OCH2CH2OCH3

11.4.
RSH R1SR2
. :
SH

CH3
CH3CH2CHCH2SH

CH3CH2CHCH2CH3

2--1-

3-

CH3CH2CH2SH

SH

1-

914

915

- SH - .
.

, :
C6H5SC6H5

CH3-S-CH2CH2CH3

CH3
CH3

S-(CH2)6CH3

CH3
-(1,1-)

.
- - .
,
:
CH3-S-CH2-CH2-CH-CH2-CH3
CH3
3--(1-)

CH3-CH-S-CH2-CH2-CH2-CH2-CH3
CH3
1-()

,
, - ().
- :
H
H C
H

S
H

, 1,10

, 110

S, 1,33

S, 108

S, 1,82

S, 100

, CS
. C-S ,
-O, 1,1 /.

915

916

, , H2S (Ka=7,05)
, . Ka 9,5-11, ..
- -:
C2H5SH + OH

C2H5S

+ H2O
pKa = 15,7

pKa = 10,6

S-H , O-,
.
. , ,
37 o, - 78 o.

.
10-7-l0-8 / (.. 1 50
),
. a ,
.
:
--1- 2--1-.

11.4.1.

-
-:
NaSH + RBr
CH3(CH2)14CH2Br + NaSH

20 oC

RSH + NaBr
CH3(CH2)14CH2SH + NaBr
(60%)

, , ,
-
,
R2S.

916

917

,
.

.
,
S . S-
:

C6H13Br + S=C

NH2
NH2

78 oC

C6H13S-C

C6H13S-C

NH2

Br

NH2

1) NaOH; H2O
2) HCl; H2O

NH2
NH2

Br

(90%)

C6H13SH + H2N-C-NH2 + NaBr

O

(83%)

:
O
H3C

O
+ RX

H3C

S K
HCl
H2O

RSNa + CH3COOH
S
H3CH2OC

+ RX

S K

SR

NaOH
o
20 C; HOH

RSH + CH3COOH
S

H3CH2OC

SR

1) NaOH
2) HCl; H2O

RSH

11.4.2.

. ,
():
R1S + R2 X

S N2

917

R1S R2 + X

918

- ,
-, 103-104
.
.
:
CH3(CH2)3S Na + CH3I

CH3(CH2)3SCH3 + NaI
(71%)

S Na + CH3CH(CH2)5CH3
Cl
CH3

CH

N(C2H5)3CH2C6H5Cl
H2O-C6H6; 70 oC

(CH2)5CH3
(86%)

CH3(CH2)3S Na + CH3(H2)6CH2Cl

N(C2H5)3CH2C6H5Cl
H2O-C6H6; 70 oC

CH3(CH2)3-S-(CH2)6CH3 + NaCl
(90%)

:
Cl(CH2)4Cl + Na2S

; 100 oC
H2O-C6H6; 70 oC

+ 2NaCl
S

(73-78%)

2CH3(CH2)4CH2Cl + Na2S

2(CH3)3CCH2Br + Na2S

PC6H33(C4H9)3Br
N(C4H9)4Cl
H2O-C6H6; 20 oC
PC6H33(C4H9)3Br
H2O-C6H6; 20 oC

CH3(CH2)5-S-(CH2)5CH3 + 2NaCl
(90%)

(CH3)3CCH2-S-CH2C(CH3)3 + 2NaBr
(81%)

:
(CH3)2S + CH3I

; 20 oC

918

(CH3)3SI

919

,

:
HO

+ CH3-S(CH3)2

SN2

CH3OH + (CH3)2S

, ,
, (CH3)2S
OTs-- r--.
.

R-S-S-R, RSO2H RSO3H .
, , , , n3,
:
2RSH + I2 R-S-S-R + 2HI,

2RSH + 22 R-S-S-R + 2H2O.

:
RS

SR

1) Na; . NH 3; -33 oC
2R
2) H 2O; NH 4Cl

SH

, - ,
:
O
RSH +

C
O O H

Cl

CH2Cl2
-30 oC

O
R

S
OH

- -
(
):
N

SH

HNO3; t
H2O

919

SO3H

(60%)

920

CH3(CH2)15SH

O
RS OH
O

KMnO4
H2O

RSH

KMnO4

CH3(CH2)15SO3H (36%)

H2O

:
[O]

R1SR2

R1S

O [O]

2+

R1S

R2

R2

NaIO4, -
--. 0,5
.

,
0 - (,
, ):
NaIO4

CH3(CH2)3SCH3 H O-CH OH;

2

CH3(CH2)3-S-CH3 + NaIO3

(96%)

0 oC; 16

C6H5SCH3

O
O

NaIO4
H2O; 0 oC

C6H5

(99%)

NaIO4
H2O-CH3OH; 0 oC

S O

CH3

+ NaIO3

+ NaIO3

(87%)

, -,
1,2- :

920

921

O
S

RSR + IO4

O
I

H2O

S O + IO3

-
-
:
CO3 H
Cl

0 oC

CH2Cl2

S
O

R2S + (CH3)3C-O-Cl

CH3OH
78 oC

Cl

CH3OH

R
S
R

+
(90%)

C
OH

Cl

R
S
R

Cl
OC(CH3)3

R
R

OC(CH3)3

S O + HCl + (CH3)2C=CH2

30%-
20
,
, , :

C6H5CH2SCH3 + H2O2

O
O
C6H5CH2SCH3 + C6H5CH2S 2+ CH3
(10%) O
(77%)

(nO4; N3 .):
C6H5CH2SC6H5

KMnO4
CH3COOH; 70 oC

S 2+ CH

C6H5CH2

(78%)

90-100 o
-

:

921

922

CH3(CH2)15-S-(CH2)15CH3 + H2O2

CH3COOH; 90 oC

O
CH3(CH2)15S 2+ (CH2)15CH3 + H2O
O
(98%)

22 ,
(V2O5) (WO3 H2WO4):
C6H5CH2SCH3
O

WO3
CH3COOH; 90 oC

C6H5CH2S 2+ CH3 + H2O

O
(84%)

.

.
: S+O-, , -
, S=O, d*-p d- p-
. 1,47
, S-O 1,69
.

d*-p d- . III
, S+-
SO.

.
-

,
- S+,

922

923

.
c ,
:

CH3

O
CH2CH2CH3

CH3
CH2CH2CH3

(R)-

(S)-

1926 . 3S(O)64-.
S--L- (S-) ,
. -
150-200 o,
H 35-40
/ (150-175 /), .. .
.

, .
. (. 3, . 1),
, -
. ,
, , , :

H3

CH3 + CH3OTs

CH3S

H3

CH3

CH3 + CH3I

CH3

923

OCH3
CH3

OTs

O
S

I
CH3

924

.
Pt+2, Hg+2, Ag+1, d+2 ,
, , Al3+ . -
.
-
SO SO2. -I- (. . 2, . 1)
-- - ,
, ,
, - :
O
CH3SCH3 + NaH
O
CH3SCH3 + (CH3)3COK
O
R1CH2SR2 + C4H9Li

60-70 oC

60-70 oC

0-(-20) oC
-

O
CH3S-CH2 Na + H2

O
CH3S-CH2 K + (CH3)3COH
O
R1CH-S-R2 + C4H10
Li

-C4H9Li (-37)2NLi,
-80 ,
.

, ,
.

,
.
-,
RX
:

924

925

O
R1CH2SR2

C4H9Li
-
-78 oC

RCH2X
-
0-(-20) oC

R1CH-S-R2

O
R1CH-S-R2 + X
CH2R

:
O
C6H5CH2SCH3

1) C4H9Li; -
-78 o
2) CH3I; -20 oC

O
C6H5CH-S-CH3
CH3

(88%)

SN2-
-:
O

(CH3)3C-SCH2R +

(CH3)3-S-CH-CH2-CH-R1

R1

(80-90%)

, 1,3 (., ., 1965
.):

O
O
+
1) CH3-SCH2 + RC-OCH2CH3

0 oC
-

O
O
H2-S-CH2-C-R

O
RC-CH2-S

O-CH2CH3
O
O
2) R-C-CH2-S-CH3 + CH3S
CH2
O

O
3) R-C-CH-S-CH3
O

+ CH3CH2O

CH3

O
O
RC-CH-S-CH3 + CH3S-CH3
O
+

H3O

H2O; 0 oC

O
RC-CH2-S-CH3
O

(. 17). ()

925

926

.
- 1,3-. 1,3 --
10-12.
,
1,3-.
-
:
O
O
-
CH3(CH2)4C-OCH2CH3 + 2CH2-S-CH3 0-10 oC, 30
O
O
O
O
HCl
CH3(CH2)4C-CH-S
CH3(CH2)4C-CH2-S
H2O; 0 oC
(70%)
CH3
CH3
O

-
1) CH2S-CH3 0-10 oC

C OCH2CH3

2) HCl; H2O; 0 oC

C CH2 S

CH3

(95%)

CH3CH2OOC(CH2)7COOCH2CH3

-
1) CH2S-CH3 10 oC
2) HCl; H2O; 0 oC

O
O
O
O
CH2-S-CH2-C-(CH2)7-C-CH2-S-CH3 (82%)
1,3-
Al(Hg) :
O
O
CH3(CH2)4C-CH2-S-CH3

Al(Hg)
-2O; 20 oC

CH3(CH2)4C-CH3
O

926

(98%)

927

O
O
O
O
Al(Hg)
CH3S-CH2-C-(CH2)7-C-CH2S
CH3-C-(CH2)7-C-CH3
o
(90%)
CH3 -2O; 20 C
O
O
O

S
C
CH2 CH3

Zn

C
CH3

CH3COOH; 20 oC

(93%)

, ,

1,3-,
.
. 1,3-
, NaH; [(CH3)2CH]2NLi,
- (. 17). -
-
.
Al(Hg) :
O
O
O
O
O
1) NaH; ; 0 oC
Zn
RC-CH-S
RC-CH2CH2R1
R-C-CH2S
2) R1CH2X
CH3COOH
CH3
CH2R1CH3
,
-
, 17.

, :
O
C6H5S

+ O
CH2Li

OH

; 0 -(-20) oC

O
CH2S
(77%)

C6H5

, ( ,
(SiCl4; l3; SOCl2; l3; l3 ..) -

927

928

-,
. (1909):
R1S

120-140 oC

+ CH3C-O-CCH3
CH2R2
O O

O
1
R S-CH-O-C
+ CH3COOH
CH
3
R2

R1 R2=Alk; Ar
,
,
, - .
- :
CH3COO

O
(CH3)2CH-S

+ CH3-C-O-C-CH3
CH3

O
CH 3C

-H3COOH
+CH3COO

O-COCH3

O-COCH3
(CH3)2CH-S-CH2

(CH3)2CHSCH3

-CH3COO

(CH3)2CHS=CH2

O
(CH3)2CH-S-CH2-O-C-CH3
- (69%)

928

929

12

12.1. ........................................................................................................................ 929

12.2. ..................................................... 933
12.3. ..................................................................................................................... 937
12.4. .......................................................................................... 945
12.5. ................................................ 951
12.6. .................... 955
12.7.
................................................................ 960

12.7.1. .................................................................. 960

12.7.2. ..................................................................................... 966
12.7.3. ........................................................................................ 968
12.8. ........................ 972
12.9. ...................................... 977
12.10. ......................................... 981
12.11. ......... 985

12.11.1.
....................................................................................................................... 985
12.11.2. ............................................................................................ 989
12.11.3. .............................................. 995
12.11.4. 998

12.1.
- - .
1825 . ,
. nn.
1833 . .
NaOH 66.
-
- , , ,
.
, , , , ,
929

930

, 65, ,
.


, , ,
.
., 1865 .
1,3,5-:

.

-(1,2), -(1,3)- -(1,4)-:
Cl

Cl

Cl
Cl

Cl
Cl

-
(1,2-)

-
(1,3-)

-
(1,4-

1,2- ,
, I II:
X

II

, , -.
, , 1,3,5 ,
( ):

930

931

, -, -
,
. 1,3,5-
,
.
. .
XIX .
;
.
,
- ,
[2.2.0]-2,5:

(1869 .)

(1867 .)

(1887 .)

1
. 12.1.

931

932

,
- .
- 2,8 ,
--. ,
, ,
.

.
XIX . , ,
1963 . .
-
- -
. ,
- 1,397
120. - -
sp2- ,
p-
-
. -
.
(.1), p-
-,
, - . . 12.1
- . 1
.
2 3,
. 2

3. p-,
1, 2 3
. - 4*, 5* 6* -

932

933

. 4* 5* .
6* .
.
, p-

- , :
1/

-1/ 6
-1/2

-1/ 3

6*

1/2 3

1/2

4*

5*

1/ 3
1/2 3

1/2

-1/2

-1/2 3

-1/ 3
1/ 6

(. 13).

12.2.

.
,
. 1931 .
(). 2. ,
p-,
-.
j=+ j, Ej - j-
; - ; - ; j -

933

934

, ,
, .2 (.1):

m j = 2 cos

2 j
N

N 1
2 _ _ N
j = 0;1;2...
N
_ _ N
2

N - .

, .
, ,
4 ,
.
+2, -2.

- .
- ,
.

, e. . 12.2
- , 1,3,5,7ee.
-.
- ,
.

934

935

1,41

+2

2
1,41

+1,41
+2

+2

+1,41

+2

1,41

+1,41

+1,41
+2

1,41

+2

-1,3,5,7

. 12.2. ,

4, 5, 6
. - . 12.1.
-
2(+2)+4(+)=6+8. 1,3,5- ,

- (6+6).
.
-
. 2,
18 /, ..
36 /.
.


, -
(. . 12.2)
2(+2)++=4+4, .. , .

935

936

,
, -. -
, - , .. (),
. -
, -
.
,
. , ,
.
,
, .
,

:
R
R

-,
.

(. ).
,
. e,
.
(, ) ,
. ,
-, -
-.

936

937

- ,
,
,
.
, (4 + 2) , = 1, 2, 3 .... (4 + 2)

. 4 ( = 1 , = 2
..) , .

, 4n-
-. , 8-
, -
(III), .. . ,
,
.
(4 + 2)-
.
.
(. 25 . 4).

Ill
,
,
(anula (.) - ).
.

12.3.

937

938

.
.
[4]-, - [6]-, - [8]. (. 13)
.
- -
. - (.
27, . 3) (. , 1964).
-3,4-
:

H
l
Cl

+ Fe2(CO)9

OC Fe
CO
OC

(IV)
e
.
, .
-
e,
1,3-
.
:

938

939

Ce(NO3)4

Fe(CO)3
H
CH3OOC

COOCH3

COOCH3

COOCH3

C(O)OCH3
C(O)OCH3
C(O)OCH3
C(O)OCH3

-e

- - [4.2.0.02,5]:

,
.
1972 .
-- 2 (-)
:

O
C O

h, 263

CO2

, :

C
C

O
O
O

h, 260

h, 260

939

N
N

940

-260 o [4]-.
-250 ,
-240 o .
.
- ,
(. 12.2), .. ,
- ,
.
, .
-,
, . ,
,
, ,
:
4
3 ()
2

3
2 ()
1

2 ,
(
) (
), 3 -
(. ).
, .
--
(IV) -78 .
,
:

940

941

(CH3)3C

C(CH3)3
(IV)

(CH3)3C

OOCH3

, .. [8]-,
(1943)
(. 6, . I):

4 HC CH

Ni(acac)2,
80-120 ; 10-20

(70%)

1960 .

. , . , .
. . |18]- .
.
-1,5 - (. 6, . 1)

,
.. , 1,3,7,9,13,15, -

.
[18]-:

941

942

CH2 C CH

H2
C

CH
C

CH
CH
C
CH2
CH2

Cu(OAc)2

CH2

C5H5N

CH2
C

(6%)

CH

C CH

3H2

(CH3)3COOK

Pd/BaSO4
(CH3COO)2Pb

(CH3)3COOH
55 oC

H
H

H
H
H

H
H

H
H

H
H

1%

[18]-

18 -, ..
. [18]-
- 130 o ,
.
,
: 1414 3030 .
[10]-, , ,
.
, .
-,-,,-,-

, :

942

943

-,-,-,-,[10]-

-,-,-,-,[10]-

-,-,-,-,
-[10]-

[10]- -
.
[10]- .
,
.
|10]-
, 1,6- [10]-
. .
1,6- [10]-
:
l

Cl
Na

CHCl3
(CH3)3COK

Br

NH3 .

Br

2Br2

KOH

CH2Cl2

CH3OH

Br

Br
1,6-[10]-

, (.
),
, - .
.
,

1,6- [10]-.

943

944

1,6- [10]-
.
[14]-, [10]-,

. [14]-, 1,6 8,13,
:

-1,6-8,13---[14]-

[12]-, ,
, -70 , -40
-[.4.0]-,
:
H
-100

+20

H
[12]-
+20

+50

[16]- .

- :

t o

H
h

H
[16]-

944

945

= -- [16]- ,
(. 13.8.3)
.
,
[4n+2]-
[4n]-.
n=1;2. , [4n+2] , , ..
.
[22]-, , -, [26]-
[30]-. ,
, 4n+2 ,
.
, .
, ,

, , ,
.
,
:

,
,
-
() .

12.4.
, ,
, , ,
, (4+2)-.

945

946

, t

( = 0), (n = 1)
, (n = 2) .. . 12.3
-
.
.
- , .

e. ,

, .

+0,62

+0,62

1,62

+1,25
+2

1,8

1,8

0,45

0,45

1,62

0,45

+1,25

+2

+2

1,8

0,45

1,8

1,62

1,62

+0,62

+0,62

+1,25

+1,25

+2

+2

+2

. 12.3. -

-, -
. -
- . 1957 .

- F3:

946

947

6H5C

CC6H5 + C6H5C=N=N
CN

C6H5

C6H5

C6H5

C6H5

1) (2H5)2O.BF3

BF4

2) H2O

C6H5

CN

C6H5

:
Cl

Cl

(-C4H9)SnH

Cl

SbCl5

C6H6

Cl

SbCl6

CH2Cl2

Cl

R+ (. 9).
R+, +3,1, R+ = -7,4,
.. . 1,2,3--- (R+
= 7,2) , .
, 2 , ,
-
13

1:
C6H5

C6H5

SbCl5

C6H5

Br
C6H5 SO2 (.); -60 oC
C6H5
CH3

CH3

CH3
Cl

Br

C6H5
CH3

CH3

SbCl5

CH3 SO2 (.); -78 oC

CH3
Cl

C6H5
2+

C6H5
CH3

Cl
CH3

CH3
2+

CH3

CH3

-
pKa = 15,5-16,0 , -
, , -,

947

948

--.
. 55- D5h
-- ,
- . - ,
.
-
,

.
:
Br2

H 2C5H5N

-C5H5N.HBr

Br

Br

OH

Br

+ H2O + Br

, 13,5 .
( ) 77+,
- 1,3,5- ().
. , .. ..
1954-1957 .:
Br
H
+ Br2

0 oC

H
H

1,3,5-

H
+ PCl5
H

1) CCl4
+

2) H2O

948

Br

Cl + POCl3 + HCl

Br

949

H
H

(C6H5)3CBF4

BF4 + (C6H5)3CH

CH3CN

(85%)

D7h -
, ,
.
R+ = +4,7; ,
- (C6H5)3C+ -
R+ , -6,6, (4-CH3O-C6H4)3C+ R+ = 0,8, . .
.
, ,
. [8]-,
,
. -,
:

+ 2K

2-

2K

- 1,41 ,
- .
, , , . -
,
:
2-

- -
- . ,

949

950

[6.1.0]
:
H

O
CH2S-CH3

(CH3)3COK

-- -
-,
[10]-,
.
-
- ,
, :
+
(6H5)3CBF4

BF4

CH2Cl2

H
H
[12]-, ,
-60 o, -40 o [6.4.0]. [12]-, ,

, 14- -:

2Li
; -80 oC

2Li

[12]--
.
12 - 4n- (4n +
2)- 14 -,
([8]-).

950

951

[15]--,
- ,
R+ = +8,4:
H
H
(C6H5)3CBF4

BF4

CH3CN

14 - .
[16]-- [16] SO2 CD2Cl2 -80 o.
,
, 14 -. |16] [16]--,
18 -:

2+

FSO3

FSO3H

2K

SO2
-80 oC
CD2Cl2

14

2-

18-

[24]-, 26

-, .

12.5.
(.1, .1) - -
(4n + 2)- (4n)- -
(. 12.1). , ,

951

2K

952

, ,
. ,
n,
.
(. 12.8).
, ,
4n -, .
(.2) ,
4n -
-. ,
.

-, - .
- , ,
. , , -
, - 1,3,5-.
-e -
, .
. .,
. , ,
, (. . 12.1).
[4n]-
,
-1,3 20 /. [4n]-,
([8]-), e
, , -. , 4 -,
, .
12.1
,

952

953

10

10

[12]-

14

[16]-

18

22

[18]-

18

[22]-

- 8

[10]-

10

, , - (VI),
- (VII), - (VIII)
:

VI

VIII

VII

- , , - .
- ,
, .
(
)
:
_
+e
_
-e

_
+e
_
-e

953

954

-
a 61-62, ,
(. 3). -
, ,
.
,
-:
C6H5

C6H5
NaNH2

C6H5

NH3 .

C6H5

C6H5

C6H5

C6H5
C6H5

C6H5

C6H5
C6H5

C6H5

C6H5

C6H5
C6H5

a ~50, ,
a 31,5; . . 3, . 1). a
60.
-, -,
4-. 1,24

.
,
.
F3 SbF5
- :
C6H5

C6H5

C6H5

C6H5

BF3
CH2Cl2

C6H5
C6H5

OH

C6H5

C6H5

954

C6H5

C6H5

955

- 5 -196 ,
:
SbF5
-196 oC

NBS

Br

- , -

.
-, -,
7--
7- -20 :
K-Na

K-Na

-20 oC

-20 oC

OCH3

C(C6H5)3

, -,
.
4 -.
[18]-, - [14] - (. 12.1).
- , ,
. 4
.

12.6.

955

956

(4 + 2) -
, , .

,

- ,
.

[10]- -,
-
, -.

-
, ,
, ,
- ,
, :
1

1
2

3
5

[14]- . [14]-
:
8

3
5

10

2
1

10

, , ,
(), , ,
:
956

957

10

12

11

11

12

13

14

10

4
5

12

11

10

10

9
12
11

13

14

12

11

4
5

10

7
8

, , ,
. , , ,
12, 16 20 -, .. 4 + 2,
:
1

12

2
8

10

7
6

2
3

5
4

957

11

10

4
5

8
7

958

, ,
.
, ,
, , ()
, ,
:
H
H
H

-.
.

, .
, ,

,
-:

, 10

-, - 18, 14 -,
- .
,
958

959

-,
, ,
. ,
,

.

, .

.
- .
, ,
-
,
.

.
,
, :
CH2

,
, , ,
,
.

.
.

959

960

12.7.

,
, (4n + 2) - (. . 12.1).
(4) - . , ..
.
.

.
,
, .
, ,
- ,
.
,
,
. ,
,
. ,
.

.
.
, .

12.7.1.

960

961

-


.


. ,

,
.

,

.
.
28,6
/ . 1,3,5
85,8 /:
+ H2

Pt

+ Ho; Ho = -28,6 /

49,8
/:
+ 3 H2

Pt

+ Ho; Ho = -49,8 /

, , 1,3,5, 36 /.

, .
, ,
, .
-. 36 /
1,3,5-

961

962

. -
.
1,3,5 ,

-
1,397 . ,
. ,

1,3,5-
.
, 27 /.
1,3,5-
63 /.
, .

. 12.4.
.

27 /

1,3,5-,
,

36 /

,
,

63 /

. 12.4.

962

963

,
- -
. ,
,
.

,
. (,
)
,
-
- , .

. -
().
, ()
( ),
.
;
,
. ,

, .
,
. ,


.

( ):
= (E - E)/N,

963

964

; - ; N -.
. 12.2 ;
, .
- , ,
;
- ().

, .
, ,
, , -
. , ,
. ,
- (.
12.2).
, ,
,
. , ,
.
.
12.2
;
,

()

964

0,333

0,145

0,065

965

0,368

0,132

0,055

0,380

0,114

0,047

0,389

0,138

0,055

0,385

0,101

0,042

0,388

0,091

0,038

0,407

0,131

0,051

0,404

0,131

0,056

0,336

0,017

0,023

0,244

0,008

-0,02

0,000

-0,193

-0,268

0,0298

-0,054

-0,027

0,307

0,001

-0,018

0,151

CH2

965

966

0,062

0,011

0,047

0,143

0,103

N
H

N
H

12.7.2.

. -

.

,
.

: , .
, , .

, ,
,
.

p-
( , . . 25, . 3).
-

966

967

- . ,

sp3 - sp3 1,544 ( ), sp3 - sp2 1,544 (
), sp2 - sp2 1,544 ( -1,3) 1,475 (
).
- 1,330 .
- 1,397 , ..
, .
-
, ,
.
33+, 55-, 77+.

- .
, , . , ,
(1)(2) 1,371 , (2)(3)
1,41 , (1)(9) 1,42 .
, ,
, (1)(2) , (2)(3).
(9)(10) 1,350 ,
(10)(10) 1,453 . [18]-, [22]-
- .
, -

.

:
,
,

. ,
.

967

968

- l ( ) ,
,
. ,
, ,
,
. ,
,
.

12.7.3.

H0 ,
H1=H0M, M , .
, .. , , ,
M .

, , ..
.
,
.
,
, ,
, , .

M = M(.) - M (.).
- ,

968

969

.
, M
,
(..
).


.


.
,
0. ,
, .
,
,
.
0
(. 12.5).

0,
. , , ,
0, ..
. ,

, .

969

970

. 12.5. ,

- [18]- -70
. ~9,3 ..
,

=-3 .. ,
.
[18]-.

-
1,6- [10]-, ,
. -

=7-7,2 .. -
=-0,5 .., :
H

H
H

H
H
H

H
H

H
H

CH2
H

H
H

H
H

1,6-

[18]-

970

971

.
, ,
,

. - ()

.
- [16]-.

. - -120 o
10,5 ..,
- 5,4 ..

.
, ,
, .
, , , -

,
.
,
.

,
. , ,
,
.
.

,
(. 13).

971

972

12.8.

. =-
, ,
p-, .

- == ,

p-, . , =, =N-; N+-R; =O+-; =S+-, p-

- . =-
: , ,
:
4

4
5
6

N
..

N1

4
3

O
1

4
3

3
+

(2) (6), (3) (5) , (4)

.
C(2)-N (1,34 ); (2)-(3) (1,39 ) (3)-(4) (1,40
). sp2- ,

sp2-
p-.

.
=-
: , ,
=- - :

972

973

N
N

N
N

1,2,3-

N
N

N
N

1,2,4-

1,3,5-

-=-
-O-; -S-; -Se-; -NH-; -NR-, p-
-.
:
, , :

Se

N
H

-=-
,
=- =N- -
, , :
N
O

1,3-

N
S

1,3-

NH

NH

1,3-
1,2-
()
()

N
S

1,2-

NH

N
N

1,2,4-

NH

, ,
.
:

973

974

N
H

N
H

,
.

, ,
, .
, (
) - . , ,
, () -
.
(. 13).
, .
, .
.
2,2 D, ,
1,8 D :
-

+
N

N
H
1,8 D

2,2 D

, ,
, -
. , , , ,

974

975

-, .
(, ) . - . o
. 12.2. , 5-
, ,
.
,
-, (4n+2)

- , >1.
.
-[17]-, -[17]-, -[18]-,
[18.]-:

R
O

-[17]-

-[17]-

-[18]-

N

, 1,6- [10]-,
10 -:

N
,
,
. 4n -
, , 2- :
975

976

NH

2-

.

-265 ,
-250 :
S

h; -265 oC

S
S

+ S2

, 1--,
,
:

NH

1--

,
:
O
O
,
:
N

, ,
.
V
(As, Sb) c ,
:

976

977

Sb

As

, ,
:

As

Sb

Bi

12.9.
()
,
.

.
. ,
0,5-1%
, - .
Pt/Al23
450-550 10 40 (1106 - 4106 ).

:
1) :

CH3

Pt/Al 2O3
500 ; 20

CH3
+ 3 H2

2) :

CH3

Pt/Al 2O3
500 ; 20

CH3
977

CH3
+ 3 H2

978

3) ,
:

CH3(CH2)5CH3

H2CH3

CH3
+

Pt/Al 2O3
500-550 ;
20-30

+ 4 H2

H3

, , ,
.

,
. ,
.
, 1015%, 50-65%.
,
,
. , , -
.
90% .

. .
, .

700-750 35-70 :

CH3

700-750 ;
35-70

+ CH4

-, - ,

978

979

CH3

CH3

CH3

480-500

CH3
+

H3
CH3

CH3

10-20%,

.
.
1000-1200 (75%
), (300 3 1 ), (2-4%
) . 30-40 /3 : ,
, , , , ,
. 80-170
, , , , ,
.
170-250
, 1- 2-, , , .
270-360 , , , ,
, : , ,
.
, , ,
. 8-10
, 2 , 0,3 , 40-60 , 5-10
.. , , .

- ,
:

R
+ RX

AlCl 3

979

+ HX

980

- . 13.
(1864),

:
Br

+ 2Na + CH3(CH2) n CH2Br

CH2(CH2) nCH3

20o C

.
,
.
.
.


:
ArBr + 2Na

ArNa + Na Br

ArNa + RCH 2Br

ArCH 2R + Na Br

e ,
,
.
-
- 1- :
C 6H 5Br + CH 3(CH 2)2CH 2Br + 2Na

20 o C

C 6H 5CH 2(CH 2)2CH 3 + 2Na Br

(65%)

, -
-.
,

980

981

-
:
R 1M + R 2X

R 1R 2 + MX

M=Li, Mg, Al, Hg, Sn .

,
- , , . .27.

.16:
ArC

+ Zn(Hg) + HCl

ArCH

2R

12.10.

.26 ( 4) .

.
,
XIX .
,
, :

[2.2.0]-2,5

()

()

981

982

-,
. 1963-1973 .
-, ,
.
- 2,5-
[2.2.0] - 1963 .
[2.2.0]-5--2,3

:
O
C

OH

Pb(OAc)4

O
(20-40%)

HO C O

O
h

O
O

:
CH 3
2CH 3

C C

CH 3

AlBr 3

AlBr 3

CH 2Cl2

CH 3
CH 3
CH3C CCH 3

CH 3

CH 3

CH 3

CH 3 CH 3

CH 3

982

CH 3

983

[2.2.0]-2,5 -
; 20 o ,
90 30 .
,
120 105 , 20
.
, ,
,
70 / .
.
- , ,
-
(.25, .), , ..
, 1,3,5-,
- :

,

, .. :

( )

.
- ,
.
- -
- 254 (
),
- . 254

983

984

S0
S1 - *-.
S1 . 160-205 ,
.
- - 1,3--5-. ,
S2 .

:

S2

204

254

50-60

S0

S1

CH2

1971 ., :
+ CH 2Cl2 + CH 3Li

(45%)

Li
,
, ,
48 20 .

. :

984

985

N
N

O
N C 6H 5

N N
C O

O C

N
C 6H 5
h, 35 o C

KOH

(11%)

CH 3OH-H 2O

N N
.
.

12.11.

. .
13. ,
,

.

12.11.1.

,
. - 110 /,
- (95 /).

985

986

, :
HCl + C6H5 + Ho

C6H6 + Cl

Ho=+7 /

.
. , , (, , ).
18%:

Cl
C6H6 + 3 Cl 2

Cl
Cl

Cl
Cl

Cl

.


, :

CH2Cl

CH3

CHCl2

CCl3

Cl2, h

Cl2, h

Cl2, h

- HCl

- HCl

- HCl

-
. - 87
/,

652 65 .
,
-, - (. 2,

986

987

. 1). ,
.
:
CH 3 + Cl

HCl +

CH 2 + H o
H o= -18 /

CH2Cl + Cl + Ho

CH2 + Cl2

Ho=-12 /

. - - -
- ,

:
H
CH2 + Cl + Ho

CH2 + Cl2

Cl

Ho=+24 /

.
-:
CH3
+ 2Br2

h
125 oC

CH2Br
(50%)

CH2Br

CH3
CH2Br
+ 2Br2

h
175 oC

CH2Br

CHBr2
(75-80%)

CHBr2

,
. , ,
300 44% 1--2-
56% 1--1-:

987

988
h,
300

C6H5CH2CH3 + Cl 2

6H5-CH-CH3

+ C 6H5-CH2CH2-Cl

Cl 56%

44%

,
2--1-
.
- (.4, .1) - .
-,
SO2Cl2,
:
(C6H 5COO)2
40 o C

CH 2CH 2CH 3 + (CH 3)3C-O-Cl

CHCH 2CH 3 +
Cl

CH 2CHCH 3 +

CH 2CH 2CH 2Cl

Cl (25%)

(65%)

CH2CH3 + SO 2Cl2

(C6H5COO)2
40 oC

CHCH3 +
Cl

(10%)

(80%)

CH2CH2Cl
(20%)

- .

N- l4:

C6H5CH2CH3 + Br 2

NBS (C6H5COO)2
C
CCl4, 80C

6H5-CH-CH3 (80%)

Br

,
, , .

.

988

989

SF4:
ArC

RC

O
H
O
H

+ SF 4

100-130 o C

ArCF 2H + SOF 2
(70-90%)

+ SF 4

100 o C

RCF 2H + SOF 2
(60-80%)

:
100-130 o C

RCF 3 + 2SOF 2 + HF

RCOOH + 2SF 4

SF4 ( SF4 )
.
,
(25)2NSF3,
:
COOH + 2(C 2H 5)2NSF 3

O2N

O2N

100 o C

CF 3 + 2(C 2H 5)2NH 2F + 2SOF 2

- ,
-.


18---:
C 6H 5CH 2Br + KF

18--6
CH 3CN; 20-40 o C

C 6H 5CH 2F + KBr
(100%)

12.11.2.

989

990

. ,
, ,
, (VI) ,
20-40%- .
(VI)
.
:

CH3

O2N

Na2Cr2O7, H 2SO4,
100 oC

COOH

O2N
(82-86%)

CH3

20% HNO3,
, 155oC

CH3

CH3
CH2(CH2)2CH3

CH3

COOH

KMnO4, KOH,
100 oC, H 2O

KMnO4, KOH,
100 oC, H 2O

(53-55%)

COOK + CH3CH3COOH
(46%)

COOK (80%)

-
. ,
,
.
.
.
.
-
, -
Na2Cr2O7 KMnO4
:

990

991

CH 2CH 2R K MnO
4

CHCH 2R

-H

K 2Cr 2O 7; H 2SO 4

CH= CH 2R

COOH
+ RCOOH

[O]

, , -
() , ..
:
O

K MnO 4

C(CH 3)3

(CH 3)3C

OH

-
.
.

, ,
.
.
18---
0,06 .
:
CH 3

H 3C

CH 3

K MnO4
18--6

K MnO4
18--6

COOH (100%)

H 3C

COOH (78%)

,
, , ,

-. O4

991

992

N(C4H9)4Br (95%) -
.
r3 .
(.16).

, .
:

CH3

CH3
+

H2O, H ,
C2H5OH

CrO3, H 2SO4,
(CH3CO)2O

(AcO)2CH

CH(OAc)2

CHO (52%)

OHC

, ,

:

ArCH2OH

MnO2,
, 80o

C 6H 5CH-CH(CH 3)2
OH

ArC(O)H

MnO2

80 o C

(75-85%)

C 6H 5-C-CH(CH 3)2
O

(77%)

. r (VI)
,
.

:

992

993

CH3
CH3

CH3

CrO3; 70o,
CH3COOH

(60%)

CH3

COOH

Na2Cr2O7,
250o, H2O

COOH

COOH

C-OOH
KMnO4, KOH,
50o, H2O

COOH

COOH
(76%)

(24%)

:
COOH

K MnO

HOOC

COOH

HOOC

COOH

K OH

COOH

(VI) :

O
Na2Cr2O7/H2SO4

90

O

,
(1,8--) ,
:

993

994

CrO3

HOOC

COOH

CH 3COOH

1,8-

,
, - - , .
33-35
- 18--6 - ,
:

-O2NC 6H 4CH 3 + O2
C 6H 5CH 2C 6H 5 + O2

(C 6H 5)3CH + O2

K OH
18--6
K OH

18--6

K OH
18--6

n-O2N-C 6H 4-COOH
C 6H 5C

O
C 6H 5

(C 6H 5)3COH

- -
(III) :
CH 3

+ O2

CH 3

CH 3

CH 3 + O 2

C
(CH 3COO)3Co; N aBr
CH 3COOH ; 150-200 oC;
4 (40 )
(CH 3COO)3Co; N aBr
CH 3COOH ; 150-200 oC;
4 (40 )

O
(60-70%)

HOOC

COOH

(98%)

-.

V2O5,
:
994

995

+ O2

C O

V5O5

O
C

400-450 o C

(85-90%)

,

( : , , ,
; . . 28, . 3).

12.11.3.

, .
-
.

.

120-150 o 1-1,5 107

(100-150 ). ,
,
.
Rh/C Ru/C -,
-:

Rh/C

+ H2
CH 3

CH 3

CH 3

CH 3

H
H

100 o C; 30

CH 3

H
CH 3

+
:

,
- -,
-.

995

996

996

997

,
.
,
. , , -
1,2-,

- , , , , ,
:
CH 2OH

CHO
+ H2

PtO2; 20 oC

CH 3O

(80%)

CH 3O

,
. 1,2,3,4 () ()
PtO2; ,

- -:
+ 2H 2

PtO2
CH 3COOH ; 50 oC;
4 . 105 (4 )

H
+ 3H 2

PtO2
CH 3COOH ; 100 oC;
10

..

H
+ 5H 2

Ni; 160 o C
CH 3CH 2OH ; 150

H
+

H
.

997

998

12.11.4.

. 1944 .

. -
.
-1,4
, :
Na
N H 3 .; CH 3CH 3OH ; -33 oC

1,4-
.
, -,
. ,
-
.
-
4- (. . 12.1)
.
. - 1,4 ,
.
-1,4.
,
:

H
+

Na

+ Na
H

998

(1)

999

.
+

Na

+ C 2H5OH

+ C 2H5ONa
H

H
H

H
+

+ Na
H

Na

H
+

Na
H

(2)

+ C 2H5OH

(3)

+ C 2H5ONa
H

(4)

,
1,4-. 1,3-,

, ,
1,4- 1,3-, -
. .

.
,
1 4 .
2,5--1-
:
COOH

COOH

1) Na; NH3; C2H5OH, - 33 oC

+

2) H3O ; H2O

(90-95%)

2 5:

999

1000

CH3

CH3
Na; NH3;

(50%)

C2H5OH, - 33 oC

1-1,4:
OCH 3

OCH 3

Li; N H 3; (CH 3)3COH

(84%)

2-

, ,-:
O

OCH3

O
H3O

5% H2SO4; 20 oC

to

H2O

,

.
, :

Li(N a); N H 3; C2H 5OH

CH 3O

H 3O
0 oC

CH 3O

H 2O

H
H 3O
t

,
, -,
:

1000

1001

K; NH3

CH 3

CH 3I

OCH 3

OCH 3

(93%)

OCH 3

-
.

.
1,4.
, 1,4,5,8 () 80%:
1)N a; N H 3

N a; N H 3; CH 3CH 2OH

2) CH 3OH
(80%)
1,4-

1,4,5,8-

1,6- [10]- 1,4,5,8-

12.3.
.

1,4-,
- 5,8-.
-2 2 (2-):
O

OH
Na; NH3;
C2H5OH

0-20 o
:

1001

1002

Li

(CH 3)2N H ; CH 3CH 2N H 2

(20%)

(80%)

9,10-,
1,4,5,8,9,10-.

1002

1003

13

13.1. 1005
13.2.
............................................................................................................................ 1008

13.2.1. - ................................................................................................................. 1009

13.3.
................................................................................................................................ 1014
13.4. ................................................. 1017
13.5. ............................................................................. 1019
13.6.
.................................................................... 1022

13.6.1. .................................................................................... 1022

13.6.2. ....................................................................... 1025
13.6. - ............................ 1029

13.6.4. . ........ 1034

13.6.5. 1040
13.6.6.
. 1041
13.6.7. ................... 1046
13.6.8.. -
............................................ 1048
13.6.8.. ............................................................................. 1052
13.6.8.. ...................................................................... 1054
13.6.8..
............................................................................................. 1055
13.6.9. -/- ................................................................................... 1062
13.7.
................................................................................................................................ 1065

13.7.1. ................................................................................................................. 1065

13.7.1.. .......................................................... 1065
13.7.1.. ................ 1068
13.7.1.. - ............................................................................................ 1071
13.7.1.. ........................... 1074
13.7.2. .................................................................................................... 1077
13.7.3. - ......................................................... 1082
13.7.3.a. ..................................................................................... 1083
13.7.3..
................................................................................................. 1084
13.7.4. - ........................................................... 1089
13.7.5. .................................... 1094
13.7.6. ......................................................................................................... 1098
13.7.6.. ........................................................................... 1101
13.7.6.. .................................... 1105
13.7.6.. ..................................................................... 1108

1003

1004

, ,
. -
, ,
,
.

,
.
,
+, ,

(, SO3,

Hg(OCOCH3)2 . .), : ,
.

1.
(-) NO2+, Cl2 Br2
(FeCl3, AlBr3, AlCl3, SbCl5 . .); H2OCl+, H2OBr+, RSO2+,
HSO3+, H2S2O7.

2.

(RClAlCl3, RBrGaBr3, RCOClAlCl3 .);
(ROHBF3, ROHH3PO4, ROHHF).

3.
ArN+N, CH2=N+H2, () NO+, (IV) CO2 ( ).
,

() (
), ,
(-NO2, -SO3H, COR, -CN .). ,

1004

1005

,
(+M)- (-OH, -OR, -NH2, -NR2, -O- .).

,
.

13.1.


.
1. SE2 (
substitution electrophilic bimolecular),
C - H:
H

+ H

+ E
()
(I)

- ,
() :
Ar
Ar

(CH)
HCMO

Ar

H+

E+

E+

, +,
. (I)

1005

1006

- , .
, (I) , . .
. ,
, ,
-, sp2, 1s .

.
2.

, -:
H

+ H

+ E
(-),
,
(II)

SE(Ar), . . SE-.

(=-=-C+),
.
- , -,

1006

1007

E
)

(III)

E + H

65 ,
, ().
(II) :
H

+
+

,
. ,
,
- - (CHE)

, - , , -.

(. 13.6.4), (+)-
- - , . . .

1007

1008

,

. , 66, 6D6 66
.
C6H5NO2 C6D6NO2 ,
65Br/C6D5Br. ,

, ,
, , , ,
,
.

. , , ,
, ,
. ,

SE(Ar)

-,
.
(1),
(2).

13.5.

13.2.

SE(Ar).

, ,
.

1008

1009

, SE(Ar) ,
c - :
.

.
, SE(Ar),

, :
D
+ DCl

AlCl3

(+ C6H4D2 + C6H3D3 + ...) + HCl

(13.1)

,
, .

13.2.1. -
HCl DCl ,
, - 78 ,
1:1 (.
, 1952). ,
. DCl
, , , ,
D, .. (13.1) .
, , ..
. -

-. , -,
-

DCl

HCl.

, .

1009

1:1,

1010

, (Cl2, Br2),
, .
. ,
1:1
,
- (1)-(2) (4)-(5):
Br

Ag

Br
Ag
-

HCl DCl -78

(1,3,5-) (1,2,4,5) 3-4 .
.

13.2.2. - ( )
HCl DCl AlCl3 AlBr3
. ,
- -
. ArH-DCl-AlCl3 ArH-DF-BF3
( 13.1).

-- .
- 1

13

ArH-HF()-SbF5 SO2ClF .
(II):
ArH + HF + BF3

ArH2 BF4

1010

1011

ArH + HF + SbF5

ArH2 SbF6

- ( )
. ,
67+ HF-SbF5-SO2ClF 134 ,
HF
BF3 30 :
CH3

CH3

H
BF4
H

CH3

+ HF + BF3

CH3

CH3

CH3

-15 . SbF5 BF3
SbF6-
50 .

, .. ,
-, -, - ( ) HF-BF3 ( ).
,
ArH2+BF4- . . 13.1

.
. 13.1 .
1.
.
3,3 . (), -
(-) 3,1 . ,
3- - -
2,7 . .

- -
. , 1,0 . , - 0,4 .

1011

1012

, - -
- - , .. 3
( - -).
13.1

HF 0 ,
-.
1.

pKa (ArH2+)

pKa (ArH2+)

-9,2

1,2,4-

-0,4

-6,3

1,2,3,4-

-1,9

1,2-

-5,3

1,2,3,5-

+0,1

1,3-

-3,2

1,2,4,5-

-2,2

1,4-

-5,7

+0,4

1,2,3-

-2,8

+1,4

1,2,4-

-2,9
2.

pKa (ArH2+)

65-65

-5,5

-4,0

+3,8

9-

+5,7

CH3

+5,8

+7,6

1012

1013

-3,5

-1,7

+2,1

2. ,
. .
-

.
:
CH3
CH3

H BF4 0 oC
CH3
C2H5

BF

+ C2H5F -80 3oC CH3

CH3

CH3

CH3
CH3

+ CH3CH3C
CH3

CH3

CH3

CH3
AgBF4
CH3NO2
-60 oC

H
O BF4
C
CH
CH3 2 5

CH3

CH3
CH3

O
C2H5

(93%)

CH3

H
+ NO2 BF4

NO2

( -)

1013

C2H5
CH3 (90%)

1014

NR2
EX

R2N

R2N

NR2

NR2
H
E

(
)

NR2

E = CH3; C2H5; (CH3)2CN; (C6H5)2CH; Cl; Br; CH3CO;

C6H5CO; CH3SO2; ArSO2; X = Hal

13.3.

SE(Ar)-

( ),
.
, 13.5 -
.
- -
,

.
. 13.1

(ArH)

ArH + E

H +
(Ar E )

- (1)

(=0)
+

ArE + H

- ()

(Ar-E)

- (2)

(=1)

- - 1
-, 2 - -.

1 +, 2 -
(ArE) .
-.
,
- 1.

1014

1015

. 13.1.
. -

-
(. . 2). ,
.
13.2
( . 13.1) (Br2 3)
(Cl2 3) 25 .
.

pKa

HCl (p)

(. 13.1)

lg (/)

Br2

Cl2

CH3

0,18

2,9

2,78

1,2-(CH3)2

0,26

3,9

3,72

3,62

1,3-(CH3)2

0,31

6,0

5,71

5,60

1,4-(CH3)2

0,22

3,5

3,40

3,30

1,2,3-(CH3)3

0,38

6,4

6,22

5,90

1,2,4-(CH3)3

0,35

6,3

6,18

5,84

1,2,5-(CH3)3

0,42

8,8

8,28

1,2,3,4-(CH3)4

0,43

7,3

7,04

1015

1016

1,2,3,5-(CH3)4

9,3

8,62

8,68

1,2,4,5-(CH3)4

7,0

645

(CH3)5

0,44

9,6

8,91

8,86

-,

,
-

,

(. 13.1)
-.
- (. 13.1), ,
. -,
-,
-.
, -

(. 13.2),
(. 13.1). ,

-.
. 13.2 ,
-
. ,

,
(. 13.2). ,

.

1016

1017
pKa

1,2,3,4,5

10

1,3,5

1,2,4

1,2,3,5

1,2,3,4
1,2,4,5
1,2,3

1,3

5
1,4

1,2
pK

1
0

0
0

10

. 13.2. ,
- ( ) -
().
.

HCl
,
108 (. 13.2). ,
.

, ,
, .

, .
, ( ),

13.4.

,
,

1017

1018

-, .. ,
-.
, (. . 13.1)
-
(. 13.3). (. 3, . 1),
, ..
, = 0 = 1 (. . 13.1).
,
.
, , ,
,
( ) -.
, -
. ,
, -,
,
.

. 13.3.

, ,

, .

1018

1019

:
H

E +

- -
, , , - -
(. . 13.3).
, - - .

13.5.

() .
13.1,
. ,
, ,

.
, ,
.

. 3.
.
, :

,
.
, ,
.
1019

1020

. ,
.

, .
.

( ):
k1

ArH + E

k -1

ArHE + B

k2

ArHE

(13.3)

ArE + BH

(13.4)

(. 3, . 1),
:
k =

k1 k 2 [ B ]
k 1 + k 2 [ B]

k2[B] >> k-1, k k1, .

k2 c k-1, k
k2. , k2[B] ,
. , [B]
,
. 2--6,8-:
N2

SO3 D(H)
O

SO3

O3S

Cl
O

N N

O3S

Cl

, kH/kD 6,0
0,0232 3,6 0,905 .
,
13.3 13.4 k2[B] > k-1. k-1/k2

1020

1021

. ,
-.
100%-
,
,
-,
k-1. , 96%-
, .
- (k1).

-,

, (. 13.7.6).
, .
1.

(-

).
2. , ,
, .
3. -
. ,
, .

(. 13.7).

1021

1022

13.6.

13.6.1.

, -,

65

+
. (
),
, (
), .
:

-, -, - -12:
X

X H
+

H
E

E
-

E
+

H
-

,

.
,
,
.
-, - -

),

+. ; ,
:

12

(. - ), - -,
, , .
1022

1023

HgCl
DCl

+ HgCl2
OCH3

OCH3

- =Alk, Br Cl.
(X = OH, NR2, NO2, CN, COR, F) -
,

+.
+ sp3-
:
NO2 < i-Pr ~ SO3- < t-Bu ~ Ar-N=N < NO < H < HgCl

. +,

.
- , ,
- .
,

- (. 26, . 3).
- -
+, -,
-
(- -):
X

E
~E

+ E

E
H
-H

--

--

E
~X

X
H

E
X

-H

--

(. ):

1023

1024

CH3

CH3

CH3
CH3

CH3
+H

-H

+H

CH3
CH3
+
H

-H

CH3

+
H

CH3

H
+

CH3

~CH3

CH3

~H

CH3

CH3

CH3

~H

~H

-H

CH3

CH3

+H

CH3

~CH3

+
H

CH3

, -
, ,
, , -,
, , -, - .

-
() -, -, - -
66+ ( ):
H
XC6H6 +

H,
/

XC6H5 +

H
+

(13.5)

(-, -,
- -)

67+.

H , H
- .

1024

1025

H, .
. 13.3.
13.3
(13.5) (/)

H, /

()

Li

62

32

25

36

BeH

14

CH3

-1

NH2

-23

24

-2

27

OH

-22

15

-5

15

-25

-8

CN

-14

-15

-15

CHO

-3

-5

-3

NO2

-36

-20

-18

-22

,
.

-.
(. . 19):
, , , ,
, .

-, - -
.

13.6.2.

65
, .
65 66, :
(65 , )

1025

1026

,
65.

,
, .

. XIX XX .
, 25
. , .

.
-.
-.
I , II .

I :
OH, OR, OCOR, SH, SR, NH2, NHR, NR2, NHCOR, -N=N-, CH3, CH2R,
CHR2, CR3, CH2Cl, CH2OH, CH2NH2, CH2NR2, CH2COOH,
CH2CH2COOH, F, Cl, Br, I

II :
SO3H, NO2, COOH, COOR, CONH2, COCl, SO2R, NO, CHO, COR, CN,
CCl3;
CF3, NH3+, NR3+;
+

PR3, +SR2, +SAr, CH2N+R3;

POR2, B(OH)2
,
, . ,
:
CH2F, CHCl2, CH2NO2, CH2CH2NO2, CH2CH2N+R3, CH2P+R3, CH2S+R2
.
I II
:

1026

1027

OCH3

OCH3
Br2

CH3COOH

OCH3
Br
+

Br
Br

(4%)
(96%)

Br

Br

Br
Br

(86%)

(13%)

(1%)

CH3

CH3

CH3

HNO3, H2SO4

NO2

NO2
NO2

98%HNO3, H2SO4

NO2
+
NO2

NO2

(1%)

(6%)

(93%)

CH3

CH3

CH3

SO3, H2SO4

SO3H
+

0 oC

SO 3H

SO3H

(43%)

(53%)

N(CH3)3

NO2

NO2
+

100 oC

(4%)

(59%)

(37%)

CH3

NO2
+

30 oC

NO2

Br
+

FeBr3

(0%)

Br

Br

Br2

CH3

OCH3

N(CH3)3

HNO3, H2SO4

+
NO2

(11%)

1027

N(CH3)3
NO2
+

(4%)

N(CH3)3

NO2
(0%)

(89%)

1028

COOH

COOH
HNO3, H2SO4

COOH

NO2

NO2

COOH
NO2
+

(1%)

(19%)

(80%)

, -
.
, ,
107 ,
.
. 1,3,5- 1,3 150
, 45%.
,
.
-. ,

.
I , ,
- .
- - . - R2N, NHR, NH2, OH,
OR, OAc SR.
.
.
,
,
:
1) -- ;
NR2, NH2, NHR, OH, OR, NHAc, OAc, Alk .
2) --
F, Cl, Br I.

1028

1029

3) - NO2, NO, SO3H,

SO2R, SOR, C(O)H, C(O)R, COOH, COOR, CN, NR3+ .
- -,

- .

13.6.


. ,

(-). 65

- - - .
-
, ,
2 3-
:
OCH3
E

OCH3
E

OCH3
E

OCH3
E

-
, ,
:

1029

1030

OCH3

OCH3

OCH3

OCH3

3-
- -
.

- ;,

, :
OCH3

OCH3
E
H

OCH3
E
H

E
H

, -
(-I)- 3. -, - , . 13.4 .
, ,
- , (+M)-.

1030

1031

. 13.4. () , ()
, () ()

. - -
,
,
(. . 2). - -

,
:
CH3

CH3

CH3

1031

1032

CH3

CH3

E
H

CH3

E
H

E
H

-
:
CH3

CH3
E
H

CH3
E
H

E
H

3, . -
,
,

-, - . 13.4 .

,

.

:
Cl

Cl
E
H

Cl
E
H

E
H

-
. -

1032

1033

,
:
Cl

Cl

E
Cl

Cl

Cl

Cl

Cl

E
Cl

E
H

,
,
.
- (. 13.4 ).
-
.
-, - - :
O
N

O
E

H
O

H
O

O N O

E
H

O
E
H

1033

E
H

1034

C+-NO2d-.

.
- ,
. -

. , -
- -. ,
- (. 13.5 ).
.

13.6.4. .

. . 1930-x .
-,

- - 65 .
, 30 oC 27
, 58,1% -; ,
- 47:
58,1
fo = 27
100

2 = 47
6
(6
2 - )

38,2% - 3,7% ;

f=27.

38,2 6
. =62
100 1

1034

1035

f=27.

3,7 6
. =3
100 2

,
(. 13.5 ).

:
C(CH3)3

CH3

47

5,5

4
75

62

Cl

0,14

0,29

0,06

0,14

0,00
0,8

COOC2H5

4,62

0,03

0,009

0,95

CH2COOC2H5

Br
0,03

CH2Cl

0,0011

0,0026
0,0079

1,16
10,4

0,11

0,0009

,
,
-.
, 3-
. - . fo

- , ,
, -
-.

()

()

.
,

.

1035

1036

-, - - ,
. ,

.
-
. ,
,

-
.

(Sf),
fn/f :

Sf = lg

f n
f

,
f . Sf
fn ,
- .
. . 13.4
,

.
13.4
, f, fn, f
( )

1036

1037

fn

Sf

606

600

2420

5,5

2,644

344

6117

820

4,95

2,219

128

4,5

749

4,8

2,195

117

32,6

626

4,9

2,107

156

253

421

3,8

2,044

59,5

103

145

3,1

1,670

36

76

59

2,5

1,373

20,6

134

32

4,0

1,311

20,5

38,9

45,7

2,3

1,363

7,7

6,8

30,2

2,1

1,160

6,5

5,7

23,0

2,2

1,014

5,5

9,5

11,8

1,7

0,842

1,75

1,8

5,1

1,4

0,554

1,6

0,0

6,6

1,6

0,625

Br2 3, 25
.

Cl2 3, 25
. CH3COCl,

AlCl3, ClCH2CH2Cl, 25
. C6H5COCl,

AlCl3, ClCH2CH2Cl, 25
.
D2O, CF3COOD, 70
.
HF, BF3, , 20
.
HOBr, HClO4,
50%- , 25
.
HOl, HClO4,
50%- , 25
.
HNO3 CH3NO2, 25
.
C6H5SO2Cl, AlCl3, 25 oC
.

Hg(OAc)2, AcOH, 25
.

CH3Br, GaBr2, , 25
.
(H3)2CHBr, GaBr3,

-.
(H3)3Br, GaBr3,, 25

-
-.
,
. , , .
1037

1038

, , , ,
, -
.
21-32% -,
-
0,3%.
, . 13.4,
lgfn Sf (. 13.5). ,

. ,
.
-, - -,

.
lgfn
4

(Br2 CH3COOH)

(CH3COCl, AlCl3)

(Cl2 CH3COOH)

(F3COOD)
(HF, BF3; HF, SbF5, 20 oC)
(HNO2, 45 oC)

(Hg(OAc)2)
1

(CH3Br, GaBr3)
(C2H5Br, GaBr3)
(i-PrBr, GaBr3)
1

Sf

. 13.5. (lgfn)
(Sf)

.

.

1038

1039

,
.
.
,
,
, .
, .

.
-

(. 13.6.7).
, ,
NR2, OR, OH, NH2 ..,
fn f, fn , f .

,

f .
-() 0,5%.
, -
-
.


.
, ,
103-104.
( )
HlO4:
D

OCH3
D

OCH3

OCH3

D
D

1039

1040

6.104

2.104

0,3

:
T

CH3

CH3

CH3

1460

36600

1340
1

CH3

1900

78800

CH3

CH3

13.6.5.

.
I II
- , - I II .

:
CH3
CH3

CH3

+ Br2

CCl4
10 oC

Br (80-82%)

CH3

CH3
HO

CH3

NO2

HNO3
(CH3CO)2O

HO

NO2

(43%)

O2N

-, - -
:
CH3

Cl
(4%)
(96%)

COOH
Br

(>99%)
(<1%)

Cl

(80%)

NO2

1040

CH3
(9%)

(59%)

(20%)
0

(32%)

Cl

1041

, :
1) -- (NR2, NHR, NH2, OH,
OR);
2) ;
3) -.
,

..

--

-, :
COOH

OCH3
F

(66%)

(87%)

(13%)

(3%)

Br

(31%)

,
,
:

(21%)
(43%)
(17%)

COOH
COOH (2%)

CH3

CH3
Cl

(58%)

(19%)

(42%)

Cl

(50%)

NHCOCH3
OCH3

(14%)

(50%)

(84%)

,
NHCOCH3-
.
.

13.6.6.
.

3 (. 3.4.3) ,

. ,

1041

1042

( ) ,
,
,
. ,
,
- (-)- -
n- (. . 3):
O

O
N

O
N

CH2

O

NO2 O 2 ;
n-(NO2) = 1,28

NO2 c COO ;
n(NO2) = 0,78

1960-

( ,

..),

.
- (
), -
, ,
.
n(2), 0,76 1,33,
(n(2) = 0,78

n-(2) =1,28) .
, ,

SE(Ar), -
- , -
(
), -. +

1042

1043

.
+

- - (,-)
90%- 25 (., 1958):
CH3
-
C Cl
25 oC
CH3

C
X

CH3
CH3

H2O

CH3
C OH + HCl
CH3

SN1
,
,
,

-:

CH3

E
X

CH3

(-4,54),

+ -. . 13.5
, n n+
. , n+
n (-)-,
. (-) n+ n ,

- + . . 13.5 .
13.5.
+

1043

n+

1044

=+-

n+

=n+-n

()

0,000

0,000

0,000

0,000

0,000

0,000

CH3

-0,069

-0,066

0,003

-0,170

-0,311

-0,141

C2H5

-0,07

-0,064

0,006

-0,151

-0,295

-0,144

(CH3)2CH

-0,08

-0,06

0,020

-0,151

-0,280

-0,129

(CH3)3C

-0,10

-0,059

0,041

-0.197

-0,256

-0,059

C6H5

0,06

0,109

0,049

-0.010

-0,179

-0,169

0,337

0,352

0,015

0,062

-0,073

-0,135

Cl

0,373

0,399

0,026

0,227

0,114

-0,113

Br

0,391

0,405

0,014

0,232

0,150

-0,082

0,352

0,359

0,007

0,180

0,135

-0,055

OH

0,121

-0,370

-0,920

-0,550

OCH3

0,115

0,047

-0,068

-0,268

-0,778

-0,510

SCH3

0,15

0,16

0,010

0,000

-0,600

-0,600

NH2

-0,16

-0,16

0,000

-0,660

-1,300

-0,640

N(CH3)2

-0,21

-0,830

-1,700

-0,870

NHCOCH3

0,21

0,000

-0,610

-0,610

COOH

0,37

0,322

-0,048

0,450

0,420

-0,030

COOC2H5

0,37

0,366

-0,004

0,450

0,480

0,030

CN

0,56

0,56

0,000

0,660

0,659

-0,001

NO2

0,71

0,674

0,036

0,778

0,790

0,012

CF3

0,43

0,52

0,090

0,540

0,610

0,070

+
, . n+
. SEAr
+ .

, r
, :
lg(k/k0) = [+r(+)].
r1 -
lg(k/k0) = +, r0 lg(k/k0) = .
. ,
.
(Br2 Cl2 CH3COOH; RCOCl + AlCl3)
1044

1045

,
r1.
-
;
NHCOCH3, S-CH3, OC6H5, OR, -
.
r -, n0, a n+=-0,6.

NO2+BF4-

(+M)-

,
.
,

.

.
,
.

,
.
,
. , r
-

(
). . 13.6
.
13.6

Br2 CH3COOH, 25 C

-12,1

Cl2 CH3COOH, 25 oC

-10,0

1045

1046

CH3COCl, AlCl3 C4H4Cl2, 25 oC

H2SO4, CF3COOH, H2O

-9,1
-8,2

HOBr, HClO4, 50%- , 25

-6,2

HNO3, CH3COOH

-6,0
o

Hg(OCOCH3)2, CH3COOH, 25 C

-4,0

CH3CH2Br, GaBr3, 25 oC

-2,4

f n,

lgfn = n+

Sf = lg(fn/fm) = (n+-) ( +)

13.6.7.

,

. ,
, ,
.

65

.

.

. , , ,
,
I ,
, - -
p,- , ()
:

1046

1047

CH3

H
H
C

II (NO2, +N(CH3)3,
COOH ..),
- - (-) (-I), :
O

HO

O
+

, X = COR, CN, SO3H, CHO, SO2R,

COOR, B(OH)2 , (-)-.
, ,
, , ..:
CH3

N CH3

CH3

Cl
F

C Cl
Cl

(-I)-.
-, , -, -.

, x - - .
II
- -.
-
.

1047

1048

,
, .

.
, ,
.

13.6.8.. -

-MO (. 12),
( ) -,
.
(..
). - ,
,
,
. ,
- (. . 12.1).
, ,
66 .
, -

.
, -,

- -.
- 65 -
, ,
:

1048

1049

-,

, - 65 .
- (n) , ,
(n-1)/2 , (n-1)/2 ,
,

65

() .
,
,

(. . 2, . 1).
- 65 13.6.
,

. -
(S). - (1, 2, 4 6)
, (3 5) (A).
, 1-p, 2-p, 4-p, 6-

p, 3 5 66 65
13.

13

.
1049

1050
6'
6
S

4'
5

5 A
4 S

px

3 A
3

2 S

2'
1
S

1'

+
1

+
2

+
3

. 13.6. - 65

px 1 px
, 13.6 1,

1 , 1. px 2
2 ( px) ( 2).
px 4 px ( 3), 4
, 4. ,

px 6 4 6.
, px
1, 2

4, 6. 1, 2, 3, 4

(
, . 2).
65: 1, 2, 3, , 4, 5, 6.

1050

1051

,
, ,
(, )
(. 2).
,
(. 2),

() , .
:

1'

2'

4'

6'

.
(.. ),
, , ..
, ,
.
. ,
,
. , , ..

, , ,
(. . 2, . 1).
4 , - . :
2/ 7

-1/ 7

-1/ 7

.
- ,
.. - 4 ,
- -

1/ 7

1051

1052

13.6.8..
,

-. ,
.
.
. 13.6 1
.
- ,
. ,
, , .
13.8. ,
2,
( 2
, ), . 13.6 (
, ) ,
, . ,
, . 2
, 2 3
(. 13.7).
,
, .. 65
. ,
.

1052

1053
X

2'

3
2

px

1
1'

. 13.7. -
,

, ,
( ; . 13.7).
, .

65N2, NH2 .

. 13.8, . 13.7.
.
1. 1 (23 /) ( )
. ,
.
2. 3 ,
(2 3) . , 3
- - .
3.
. ,
.

1053

1054

2'

NH2

-8,30
3

NH2

-9,24
2
-9,30

NH2

-10,49

. 13.8.

13.6.8..
-
, (-NO2, -COR, -SO3H .).
, -. ( ),
4 5 ,

, ,
- ,
. x

, . 13.6.
x , , ,
, 3. ,
- (. . 13.7):
X
-0,5
-0,5

. 13.9
.
1054

1055

( 0,7 /), 0,6 (19 /)

, . ,
,
.

NO2

2
-9,30

-9,87
3'
2'
-9,90

NO2

. 13.9.

13.6.8..

(. 2), ,

, .
,
- ArH +,
.
-

()

().

1055

1056

OH

NH2

0,19
0,10

0,11

0,14

0,04
0,26

SH
0,12

0,08

0,03

0,02

0,22

0,16

- > - > - > -.

-,

--

(+)-.
, ,

,
, . 2,
,
.
, .
, .
, ,
,
, .
:
, ,
, ,
.
-, , -
. , 13.6, -
- , ,
OH+, NH2+, SH+, Cl+, F+.
- ,
-:

1056

1057

X
E
H
X

-H

E
E

-H

X
H

--

o--

- ,
.

(. . , 1981).
, + ( )

:
CH3

CH3

CH3

CH3

OH

H2O2-FSO2H-SO2Cl2
-78 oC

OH
(-, -, -) OH
(71%)
(6%)
(23%)

-.
, -:
F

OH

H2O2-FSO2H-SO2Cl2
-78 oC

+
OH
OH

(-, -, -)
(24%)
(3%)
(73%)

, ,
- -.

(-> - > -), (- > - > -).
1057

1058

,
, ,
, - .
, -:
X

" "
4

" "

(2) ,
- (2) (1).
(2),
-, -:
X
X

OH

OH
-

OH

H
OH

13.6.1, -, ,
. , -.
: (1)-(2),
-,
, -. -
, , -. ,
: , ,
-.
:

1058

1059

HO

CH3 OH

1,2-

CH3

OH

CH3
H OH
~CH3
-H

CH3

4
3,4-

CH3

CH3
OH

CH3
~CH3

CH3

H -H
OH

OH

CH3

H3

~CH3
-H

H3

OH

CH3

OH

CH3

OH

CH3

~CH3

CH3

-H
H

OH

OH

OH

OH

(2)-(3) ( (5)-(6)),
2,3- . , - 3,4- ( ). ( ) 12% - .
-1-13:
OH

CH3
*

H2O2-FSO2H-SO2Cl2

-78 oC

CH3
CH3
+

(12%)

OH

(59%)

, 59% - , ..
(1)-(2) ((1)(6)) (3)-(4) ((4)-(5)),
- (. . 13.3).
, -

- - ,

( -)

1059

1060

.
, :
H3 (+I)
(-)

(. 13.6.8)

F (-I)
(+)

(-)

(+)

~0

(+)

~0

--

~0

, .
, -, ,

.

. . ,
(. .
13.9).
:
NO2
1

NO2
0,21

0,29
0,05

6 2
5 3

0,08

0,27

II

0,7 /,
,
. I,
.
- -
( - - ),
-.
,
:

1060

1061

C6H5NO2

H2O2+HF
25 oC

C6H5NO2

(-, 37,7%, -, 62,3%)

Cl2+ HClO4+AgClO4
25 oC

(-, 17,6%,
-, 80,9%, - 1,5%)

.
,

-,

- (. . 13.3). ,
(2)-(3) -:
NO2

NO2

NO2
E

+ E

NO 2

NO2
-H

E
E

I -
( -
), -

-:
NO2

NO2

NO2
-H

, 4 / , - ( +=+; . .
13.3). , , -
(NO2, COR, CN, SO2R ..),
-

- (, C6H5COCH3 fo/fn =
6). -
II, -
.

1061

1062

13.6.9. -/-

-, -

. ,
0

:
R 6H5

CH3

C2H5

CH(CH3)2

C(CH3)3

fo

49,7

31,4

14,8

4,5

1,3

2,3

2,4

3,0

fn

60,0

69,5

71,6

75,5

f fn , fo
- 10 , , ,
.
, ,
-. , GaBr3 fo/fn
:R RBr

C2H5

(3)2

(3)3

f o/ f n

0,81

0,47

0,30

0,0

opmo-/napa-

67,5%- H2SO4 F < 1 <

r < I, .. :
6H5:
% -

F
12

Cl
30

Br

38

41

% -

87

70

62

59

-/-

0,14

0,43

0,60

0,69

, ,
. ,

1062

1063

-. -
.
-/ . ,

-:
AlCl3

C6H5CH3 + RCOCl

RCOC6H4CH3

- (%)

96

l2

11

87

Cl2CH

17

80

-
, .
-
-.
, opmo-/napa- 3:1, ..
.
, - -,
( I , a-,

II

-),

- - .
, .
C65X

-/-

-,

, -. , ,
(, N NO2+) ,
65.

1063

1064

.

65. ( X).
I
, (2)-(3) (5)-(6),
II - , X, (1)
(4) (. 13.6.9).

II
13.7

opmo-/napa- -/-,
14

-/-

65

-/-

1. : HOF + HF; 25 o

4,14

4,14

0,30

0,20

0,52

0,52

0,0

0,14

1,68

1,64

0,07

0,14

OCH3

1,51

1,57

0,10

0,003

NO2

37,7% -

31% -

63,3% -

69/0,0

2. : 12 + lO4 + AgCIO4 ; 25

3,23

3,34

0,09

0,06

0,58

0,58

0,02

0,03

OCH3

0,54

0,40

65,1% -

73,4% -

NO2

11,7

19,9% -

53,9

79% -

CN

8,0

24% -

25,5

80% -

5,3

22% -

10,9

78% -

CF3

14

, , .
1064

1065
3. : CH3COONO2 + BF3; 25o

1,95

1,55

0,10

0,03

0,12

0,09

0,003

0,002

0,46

0,59

0,01

0,01

0,39

0,30

0,02

76,7% -

X - I ,
1-2 (1-6) 3-4 (4-5).
II ,
2-3 (5-6)

--

).

(. 13.6.9.).

, .
13.7, ,
.

13.7.

13.7.1.

.
, .

13.7.1..
.

:
, ..
( NO2+BF4- CH2Cl2)

1065

1066

AcONO; ( ,
).

45-50 o.
:
C6H6 + HNO3 (.)

H2SO4 (.)
40-50

C6H5-NO2 + H2O
()
(85-86%)

,
NO2+,
HCMO (. . 2):
O

()

NO2

:
HNO3 + 2H2SO4

NO2 + H3O

+ 2HSO4

( NO2+ 1400 -1), ,

( N2O4),
- , ,
HNO3 .
NO2+
, .
,
NO2+ -
. ,
. ,
HNO3

1066

1067

. ,
( NO2+):
3HNO3

H3O

ArH

+ 2NO3 + NO2
H2O*

ArNO2 + H

HNO3* + H

( NO2+ r).
r , ..

. , ,
. H2SO4
, - .
(HNO2+
2SO4)
,
:
H
k 1 ()

NO2 +

B:

+ HB

k 2 ()

k -1

NO2

NO2

Z
:B = HSO4

-.
ape .

k2
. , 2,4,6---
:

1067

1068

CH3

CH3
(CH3)3C

C(CH3)3
H
C(CH3)3

(CH3)3C

C(CH3)3

NO2
k H/k D = 3,7

NO2
C(CH3)3

13.7.1..

, ,
. ,
600 , , 27 .

(13.3) ,
, .. , -.
,

,
-. ,
, -
, -. ,
- HCl
1,5 , - - 800 .
600 , 27
, ,
-, - -?
,
(), (1,3,5) 2,7 (
200 ).
:

1068

1069

(NO2+ BF4-, 25 oC: fn/f = 22,7; HNO3 CH3COOH, 40 oC: fn/f = 22,9).

?
,
,
-:

O
N
O

- NO2+

, -
-,

-,

. ,
,
- HCl ( NO2+),
,
- (. 13.8).

HCl .
, . 13.2
109; . 13.8
, 3:1.
13.8
1
25

Me

1, 2-()2

1, -()2

1,4-()2

1, 3, 5-()3

1,0

1,51

1,81

2,06

1,65

2,60

1069

1070

1,0

1,67

1,75

1,65

1.9ft

2,71

(
)

,
.
,
.
. ,

,

. ,
, ..
,
.
,
,

-,

C6H5CH2CH2C6H4,

. ,

, .
-, 27
,
. 2
, (.
13.2). ,
, (
). ,
,
.

1070

1071

, -
.
( )
, -

[r
NO2]+. , ,
-.

13.7.1.. -
,
, ,
, .
- (. 13.6),
unco- .
-

- -.

, , .
1,4- 1,4---
:
H(H3)2

H(H3)2
NO2

HNO3
H2SO4

CH(CH3)2

CH(CH3)2

H(H3)2
+
NO2

- , ,

:

1071

1072

NO2
CH3O

(CH3CO)2O

Br + HNO3

CH3O

Br +
(70%)

+ CH3O

NO2 (30%)

-
. 13.3, --
,
X=Alk, Br, Cl, F NO2.

unco-

, -
-.
2,3,5,6- .
-60 --
3. 0
-
4, 2,3,5,6-4- - :
H3C
H3C

OCH3
CH3 NO BF
2
4
CH3

H3C

CH3
NO2

CH3
OCH3

OCH3
CH3

H3C
H3C

-78 oC

H3C

OCH3
CH3
NO2

CH3

H3C
0 oC

(85%)

H3C
NO2

CH3

napa- (4-)
85,2% 2---; 5,3% 3--- 9,5% 4 - - .
-
. -

1072

1073

(41%)

1--4--1--4-

-2,5-, 2---
40%.

--

.
(
), .
2---.
,

2---

NO2 2,

- 1 --
-
2:
CH3

CH(CH3)2

CH3C-O-NO2 (CH3CO)2O

O2N

CH3

CH3

NO2

CH3
NO2

H
CH(CH3)2
+ H3COO

O2N

CH3CO
O

CH(CH3)2

H2SO4 (.)

CH3

CH(CH3)2

(44%)

H
CH(CH3)2
-H

-H

CH3

CH3

CH3

O2N

CH(CH3)2
-(CH3)2CH

CH3

NO2

CH(CH3)2
(44%)

NO2
CH(CH3)2
(44%)

+ CH3CH=CH2
+ H
NO2
(44%)

1073

1074

1, 10 : 5 : 1 : 2,5. ,
1,4-

.
,
- - ,
.

13.7.1..

, ,
, :
NO2

NO2

NO2
+ HNO3 (.)

100

(93%)

+ HNO3

CF3

(91%)

+ HNO3

(6%)

N(CH3)3

N(CH3)3

NO2

CF3
NO2
+

+
NO2

H2SO4

(1%)

(6%)

CF3

CF3

NO2
+

+
NO2

H2SO4 (.)

NO2

(3%)

NO2

N(CH3)3

+
NO2

H2SO4
(89%)

(11%)

NO2

(HN3+ H2S4 = 1 :
2) ( : : - :
= 1 : 27 : 38 : 38), .

1074

1075

50-70 - (33-35%) -
(65-67%).
1,3,5- 1,3-
,
. 1,3,5-
2,4,6- ( ),
70 :
CH3
O2N

NO2

O2N

K2Cr2O7-H2SO4

COOH
NO2

NO2

NO2

O2N

100
H2O

(65%)

NO2
+ O2
NO2
(70%)

(, COOH, COOR, CN .)
- ; - .
.
:
COOH

CHO

CN

COOC2H5

(19%)

(19%)

(17%)

(28%)

(72%)

(80%)

(81%)

(69%)

(9%)

(2%)

(1%)

(3%)

,
,

:
OCH3
HNO3
45

OCH3
NO2

OCH3

+
(40%)

(60%)

NO2

, ,
HNO3,

1075

1076

. , HNO3
, ,
, 2.
, - N-
(, C65NHCOCH3) - -
-,
:
NHCOCH3

NHCOCH3
NO2

NHCOCH3
HNO3

+ HNO3

H2SO4

NO2 (90%)

(10%)
20
(CH3CO)2O

NHCOCH3
NO2
+

NHCOCH3

(70%)

NO2

(30%)

, ,

20-30%-

. -
, - -
- - ,

F33
:
O2N

NH2

H2O2; CF3CO2H
CH2Cl2; 40 oC

O2N

(86%)

Cl
Cl

Cl
NH2

H2O2; CF3CO2H
CH2Cl2; 40 oC

Cl

NO2
Cl (100%)

Cl
O 2N

NO2

NH2

H2O2; CF3CO2H
CH2Cl2; 40 oC

O 2N

NO2
(87%)

NO2

NO2

1076

1077

13.7.2.

l2 > Br2 > I2.

(Fl3, Fr3, lCl3,
lBr3, Ga, Sb, Sn, Ti .). l2
r2 .
,
-, -,
, , -
. .
.
, ,
,
- (. . 13.2), , ,
- . ,
Fr3 25
o

, ,

, .
:
?
,
. ( =

k[ArH][Cl2]). , .
l- ( ) 3-
. ,

Cl , 3l,
:

1077

CH3C OH
OCl

1078

ArH + Cl2

k1
k -1

Ar H
Cl

Cl

; k 2

ArCl + HCl

.
,
r . ,
.
(. 3.3..)
( -):
=

k1 k 2
[ ArH ][ Br2 ]
k 1 [ Br + ] + k 2

k-1[Cl-] ,
,
,
. , - (r- +
r2

r3-), .

(kH/kD >
1), r-, ,
k-1[Br-] > k2, ..
(. 13.5).


, .

, [Br+...rFr3]. Fl3 FeBr3,
l2 Br2 .
lCl3 lBr3
. , ,
lBr3 ,
. AlHal3 ,
- , .
- ,

1078

1079

, .
, -, Hal2 .
1+ r+
. -
, l2 :
H
+ Cl+...Cl...FeCl3
Z

Cl

Cl

FeCl4
:B = Cl FeCl4

+ HCl + FeCl3
Z
(.
. 13.2). , FeBr3 k/k = 160.
- - ~ 2:1
-, - :
CH3

CH3

CH3
+ Br2

Br

FeBr3
25

+
Br (65%)

CH3

CH3

CH3
+ Cl2

(35%)

Cl

FeCl3

+
Cl (45%)

(55%)

FeCl3 90% 1 10% 2-. ,

7-8 ,
107 .

1079

1080

.
- - 3 : 7,
1,2,3- 1,2,4-:
Cl

Cl

Cl
+ Cl2

Cl

FeCl3
25

+
Cl (70%)

Br

Br

Br
+ Br2

(30%)

Br
Br

FeBr3
25

+
Br

Br

(86%)

(1%)

(13%)

:
NO2

NO2
+ Cl2

FeCl3
40-50

O
C Cl
+ Cl2

+ HCl
Cl
O
C Cl

FeCl3
40-50

CH3

+ HCl
Cl
CH3

+ Br2

FeBr3
25-30

NO2

Br
+ HBr
NO2 (90%)

1080

1081

O
C C(CH3)3
+ Br2

O
C C(CH3)3
AlBr3
80
(75%)

+ HBr
Br

( = -10).
fo= 617, fn = 820,
(fo= 47, fn = 62).

-.
o (=-12), fn = 2500
.

, ,
(F3I).
:
CF3COOAg + I2 CF3COOI + AgI
(CF3COO)2Hg + I2 CF3COOI + CF3COOHgI
OCH3
OCH3
CHCl3
+ CF3COOAg + I2

OCH3
OCH3

20

(85-90%)

1,2-
()

r2, 3r F3r 1 : 106:

1010.
.
, ,
-, I2.
ICl.

1081

1082

,
, -, HIO4,
:
I
H3C

CH3
+ I2

H3C

H3C

HIO4

CH3
(80%)

H3C

CH3

H3C
+ I2 + HNO3

100

CH3

H3C
(60%)

I

I2 (II) CuCl2;. ,
, :
I
CH3 + I2 + CuCl2

H3C

CH3

H3C
(70%)

13.7.3. -

.-. (1877)
.

,
: lBr3; lCl3; r3; GaCl3; BF3;
SbF5; SbCl5; FeCl3; SnCl4; ZnCl2 .

:
ArH + RX

AlCl3

ArR + HX

, ,
, (III), SbCl5,

1082

1083

SnCl4; TiCl4 ZnCl2.

lBr3 > Gar3 > AlCl3 > GaCl3 > FeCl3 > SbCl5 > TiCl4 > F3
> l3 > > SnCl4 > Sbl3.
.

13.7.3.a.
- ,
,
,
, , , .
,
. ,
lCl3
.
:
RCl + AlCl3
()
-

k1
k -1

[RCl.AlCl3]

k 2[ArH]()

Ar

AlCl4

H
R

-
(
Al2Cl7 )

ArR + HCl + AlCl3

-

(B = Cl AlCl4 , H2O
)
.

(RCl AlCl3) .

:
RCl.AlCl3

RCl

AlCl3

R AlCl3

R + AlCl4

.
,
(k1),
.

1083

1084

, .
- -
(. . 13.4 13.6), , ,
, .

.
:
Cl
Br

RBr + MCl3

Cl

M Cl

Br

Cl

M Cl

RCl + MCl2Br

R Cl

R < R < R,

.
, , ,
RXn
R = 3 R = t-,
.
RX lCl3
,

- z RF > RC1 > RBr
> RI.
.
,
:
C6H6 + FCH2CH2Br

BF3
20 C, 4

C6H6CH2CH2Br + HF
(94%)

13.7.3..


, ,

1084

1085

,
FeCl3 FeBr3 0-25 .
(6H5)3 > (C6H5)2CHX >
C6H5CH2X > 2=-2 > R3> R2 > RCH2X > 3.
-
,
. ,

e,

.
, , .
.
,
.
.
-
,

-,
-- ,
:
CH2CH2CH3
+ CH3CH2CH2Cl

AlCl3; C6H6

CH3

CH CH3
+ HCl

50 C
(35%)

(65%)

1- 2 :
CH3CH2CH2Cl + AlCl3

CH3-CH-CH3 + AlCl3
Cl

, ,

1085

1086

,
:

C6H6 + -CH2(CH2)3Cl

AlCl3; C6H6
0 C

CH3
C6H5(CH2)3CH3 + C6H5CH-CH2CH3
(32-36%)

(64-68%)

,
. -
, -
(13.7.4)
:
ArH + CH3(CH2)nC

AlCl3

Cl

CH2Cl2

ArC

Zn(Hg)

(CH2)nCH3 HCl

Ar(CH2)n+1CH3
( -,
. . 26) -.
-
-:
AlCl3

C6H6 + (CH3)3CCH2Cl

C6H6

C6H6 + (CH3)2CHCH2Cl

AlCl3
C6H6

CH3
C6H5-C-CH2CH3 + HCl
CH3

(78%)

C6H5C(CH3)3 + HCl

(76%)

-,
. 2- lCl3
0

: 63% - (-

), 25% - 12% ema-a. 25

lCl3 (2 ) l - .

HF F3
10 -.
-
,

1086

1087

,
1,3-- 1,3,5:
+ 2CH3CH2Br

AlCl3 (2 )

CH2CH3

25 C, 24

(85%)

CH3CH2

(CH3)3C
(CH3)3C

AlCl3
-30 C

+ 2(CH3)3CCl

(CH3)3C
(80%)

(CH3)3C

1,2 (. 13.6.1). -, - :
CH3
CH3

-H

CH3

H
CH3

+H
-H

CH3

CH3

1,2-
H3

CH3

+H

CH3
-H

1,2-
H3

H +H
CH3

CH3

CH3
CH3

,
-.
52-60% -, 23-24% - 16-25%

-.
,
, -, - -
.
,
,
.
1087

1088

F3, ,
:
OH

BF3
60 C

+ H2O

(56%)

(27%)

, ,
, F3
. ,
:
CH3
C CH2CH3
CH3

BF3

+ (CH3)3CCH2OH

C6H6

- -2 -3 -
F3 2- 3-
2:1:
CH3-CH-CH2CH2CH3
BF3, C6H6
0 C

OH

CH3-CH-CH2CH2CH3 +
C6H5

CH3CH2-CH-CH2CH3
OH

(67%)

+ CH3CH2-CH-CH2CH3
C6H5 (33%)

- ,
,

2 : 1
2-.

,
. ,
- :

1088

1089

H3PO4.P2O5

S, t oC

+ H2S

OH
-2

CH2

HO CH2

- , ,
. ,
. lAlCl3; HF F-BF3; 3O4:
H PO

4
+ CH3CH=CH2 250 3; 25

AlCl ; HCl

+ CH2=CH2 80-1203 ; 10

CH(CH3)2

CH2CH3

NO2, NO, CN, COOR .,

-. , e
- ,
.
.

13.7.4. -

-.

,

1089

1090

.
-- 1 : 1 1 : 2.
, ,
,
, .

RC

O
Cl

RC

+ AlCl3

O-AlCl3

RC O AlCl4

Cl

, 3+=

lCl3 1:1.
RC+=O SbF5X- ,
:
RC

O
F

+ BF3

0-(-30)oC
CH2Cl2

RC O BF4

,
(RCO+, l.lCl3, RCOCl.Al2Cl6) ,

-.
, ,
.
e,
(,
e .), ,
( , )

1090

1091

-
RC

O AlCl3
Cl

H
+ RC
Z

R C O AlCl3

C O

O AlCl3
Cl
R

AlCl4

+ HCl
Z

+ HCl + AlCl3
Z

, , lCl3

, -
( ).
, lCl3 .
- ,
.
,
( ,
- NO2, CN, COOR).

. ,
.
-
, ,
, .
, ,
.

1091

1092

, 1,2-
, :
C6H5CH3 + (CH3C

C6H5OCH3 + CH3C

AlCl3
C6H5CH3

)2O
O

AlCl3

Cl

C6H6

n-CH3C6H4COCH3 (85%)

n-CH3OC6H4COCH3 (88%)
COCH3

AlCl3

+ CH3COCl

(92%)

CS2
AlCl

3
+ CH3COCl
CH2Cl2

COCH3
(90%)

COCH3
AlCl3

(70%)

+ CH3COCl CH Cl
2 2

,
F3SO3 .

:
C6H6 + CH3C

60 oC

+ CF3SO3H

C6H6COC6H5 (90%)

Cl

CH3OC6H5 + CF3SO3H + n-NO2C6H4COCl

n-CH3O-C6H4CO-C6H4-n

(84%)

.
,
I ,
-:
X

+ AlkC

AlCl3

Cl

1092

O
Alk

1093

-/- 0,03
0,01-0,03. -
0,5%.

-. -
,

opmo-/napa- 0,1 0,8. ,

AlkCOCllCl3,
-.
, , ,
.

-.
,
:
AlCl3

Cl

1-

CH2Cl2

O
O

CH2 C
O
+
CH2 C
O

Zn(Hg)

AlCl3

HCl

OH

H3PO4

-
(75-85%)

OH

-.

.

1093

1094

13.7.5.

, .

.
, .
. . 1897 . (II)
- - ,
(I):
ArH + CO + HCl

AlCl3
Cu2Cl2

ArCHO + HCl
(70-90%)

: ,
l
l,
- .
,
, ..,
-.
100-200
Cu2Cl2 Cu2Cl2:
CH3

CH3
CH3

AlCl3

+ CO + HCl
CH3

Cl

+ CO + HCl

CH3

Cu2Cl2
40 oC

AlCl3
Cu2Cl2
50 oC

CH(CH3)2 + CO + HCl

CH3

(80%)

CHO (70%)

Cl

AlCl3
30 oC
50

1094

CHO

HCO

CH(CH3)2
(60%)

1095

ape
l
:
ClSO3H + HCOOH HCl + CO + H2SO4

l N-
, -50 l :
N

N
+ HCl

+ HC

CH2Cl2

N
H

CHO

O
Cl

.
:
O

H C O

C CH3 + HF
O

ArH + HC

0 oC

O
HC
F

BF3

+ CH3COOH

ArCHO + HF

, -

-,

. ,
, , N,N-
l .

HCN

.
, .c ,
. l
HCN ,

1095

1096

.
:
OH

OH
Zn(CN)2 + HCl
0 oC

HO

CHO (85%)

HO

OH

OH
CH3

CH3
Zn(CN)2 + HCl

HO
(CH3)2CH

CHO (99%)

HO

(CH3)2CH

,
HCN, HCl ,
, , HN=CH-N=CHCl,
- .
, ,

1,3,5-.
, ,
,
:
N
ArH + N
N

HCl
AlCl3

ArCH=NH2 Cl

H2O, H

ArCHO + NH4Cl
(55-90%)

,- :
ArH + ClCH2OR

TiCl4
CH2Cl2; 20 oC; 15

ArCH

OR H O
2
Cl

ArCHO
(70-90%)

, , .

, , , - . ,-

1096

1097

:
HCOOR + PCl5 CHCl2OR + POCl3.

-, - ,
, 1927 . . . . N,N-
- N- -

.
- NR2; OR.
,
- - l3,
SOCl2 COCl2.
-

, :
O

+ Cl
HC
N(CH3)2

P
Cl

[(CH3)2N CH O

Cl
Cl

(CH3)2N CH

Cl

(CH3)2N CH PO2Cl2

O
O

O
PCl2] Cl

P Cl
Cl

Cl

( )

, ,
2 (CH2)2N+=l Cl-.
:

1097

1098

(CH3)2N

+ ClCH=N(CH3)2

(CH3)2N

CH N(CH3)2
Cl

CH3COONa

(CH3)2N

H2O
H2O

(CH3)2N

H2O

CH N(CH3)2

CHO

(99%)

,
NR2-, OR- -.
- ,
, .,
, , , . . 13.9

, .
, , , , .

13.7.6.

SO3H

:
ArH + HOSO3H

ArSO3H + H2O

.
98-100%-
(), 92-94%- ( ),
, 20 60% ,
; SO3 SO2
SO3 .
1098

1099

( ), .

.
:
ArH + ClSO3H

ArSO3H + HCl

, .

:
ArSO3H + ClSO3H

ArSO2Cl + H2SO4
13.9

; l

AlCl3

150

l23

; 85 %
o

TiCl4

212; 20

; 80 %

AlCl3

20 o

; 31 %

AlCl3,

50 o

n- ;

N
N

; l

Cu2Cl2

85%
o

l23

212; 20

- -
2:3

A1C13

20 o

- ; 81%

A1C13

100 o

- ; 90%

N
N

HCN; l
;l

AlCl3,

40

2,4,6--; 80%

Cu2Cl2

l23

TiCl4

212; 0 o

2,4,6--; 88%

HCN,HCl

A1C13

2,4,6--; 13%

A1C13

212; 20 o

2,4,6--; 92%

N
N
N

1099

1100

;l

, 40 o

4-; 73%

SnCl3

212; 20 o

4-; 80%

A1C13

CHCl2Cl2

4-; 63%

A1C13

2,4-; 89%

AlCl3,

40 o

2,4-; 46%

AlCl3,
Cu2Cl2

l23

N
N
N

N
N
N

;l

Cu2Cl2

HCOF

BF3

212; -30 o

1-; 73%

l249

TiCl4

212; 0 o

1-; 79%

A1C13 ; 20

1-; 55%

N
N

l249

TiCl4

212; 0-20 o
o

A1C13 ; 20

9-; 86%
9-; 55%

N
N

POCl3

, 20 o

9-; 84%

l249

SnCl4

212; 20 o

9-; 92%

A1C13

9-; 64%

N
N
N

l249

TiCl4

212; 0-20 o

9-; 88%

l23

SnCl4

212; 0-20 o

; 73%

A1C13

20

POCl3

; 67%

N
N

; 21%
o

HCl

Zn(CN)2

; 40

; 94%

2-

ClCH2OCH3

SnCl4

212; 20 o

2--1-;
82%

2-
2--

ZnCl2

, 20 o

POCl3

, 20

2--1-; 90%

HCN, HCl

A1C13

; 40 o

4-; 30%

HCN, HCl

2--1-; 96%

POCl3

, 20

4-; 85%

HCN, HCl

ZnCl2

, -5 o

2,4-; 70%

Cl2CHOCH3

SnCl4

212; 0

1100

2,4-; 68%

1101

A1C13

, 20 o

2,4-; 77%

POCl3

, 20 o

4-; 85%

POCl3

, 20 o

2-; 78%

N
N
N

POCl3

, 20

3-; 97%

, 4-5 lSO3. ,

- , ,
., ,
, :
+

N.SO3

O
+ O
NH
CH3O

+ O

O.SO3

100 oC
8

0-20 oC
ClCH2-CH2Cl
20 oC

O.SO3 H Cl
2 2

(93%)

SO3H
(98%)

NH

SO3H

CH3O

SO3H
(100%)

.

110-180 .
-.

13.7.6..

.
,

, 2/SO3.

1101

1102

80%
:
H2SO4 + H2SO4

H3SO4 + HSO4

H2SO4 + H2SO4

SO 3 + H3O

+ HSO4

85-98%
:
3H2SO4

H2S2O7 + H3O

H2SO4 + SO3

+ HSO4

H2S2O7

100%- H2S2O7
- 2S3O10; H4S4O13 ..
.
80%
H3SO4+.
85%
H2S2O7. , -,

. SO3,
H3O+ . 85%-
100%- H3O+ ,
H2SO4 . 91%- [H3O+]=[H2SO4],
H2S2O7 , 3SO4+,
91%-, 85%- .

, , 3SO4+. ,
:
ArH + SO3.X

(1)
+

X = H3O H2SO4

Ar

+ X
SO3

(2)

ArSO3H + X

kH/kD
95% , 98-100%- H2S4
1102

1103

kH/kD
1,15-1,7, .. (2).
95% -
- HSO4-,
H2SO4.
(2) , ec .
.
, -, SO3:
ArH + SO3
H2SO4
(3)

(1)

Ar

(2)

SO3

Ar

H
SO3H

ArSO3H + H3SO4

(2),
o.

,
. H3SO4+ H2S2O7
SO3.
, , - ,
.

,
, .
-, - -
, -,

- - -
, ,
. , ,

. 20 -

-. 100
-. - -
1103

1104

80-90%- -.
, - , . -
, , -

. , -
.
- 92-98%-
0

:
OH

OH

OH
SO3H

(10%)

98%- H2SO4

98%- H2SO4

20 oC

100 oC

(90%)

SO3H
OH

OH
SO3H

(49%)

+
(51%)

SO3H

100%-
43% -, 4% - 53% -, 100
:
13% -, 8% - 79% -.

:
SO3H
SO3H

98%- H2SO4
5 oC
-10 oC ClSO3H
ClCH2-CH2Cl SO
3

SO3H

96%-
160 oC
H2SO4

(16%)

(84%)

SO3H
SO3H
+

(100%)

(10%)

(90%)

1104

1105

1-.

SO3 0...-10.
96%- H2SO4 :
2-.

13.7.6..

. 92-94%-
40-50 90-96%.

104 , -
20%- 100
60%- 60-80

. -

90%- 235

66%

34%

:
SO3H

SO3H
90%-

20%-
SO3
100 oC

SO3H

+
SO3H

H2SO4
235 oC

(90%)

SO3H

SO3H

(34%)

(66%)

1,3,5-

60%- 250
.
,
, - ().

.
:

1105

1106

4H3CH=CH2

CH3CH-(-CH2-CH-)2-CH=CH-CH3

CH3
CH3
CH3CH-(-CH2-CH-)2-CH2-CH-C6H5

C6H6; AlCl3
0-20 oC

CH3

CH3

CH3

CH3CH-(-CH2-CH-)2-CH2-CHCH3
C12H25

CH3

15%- SO3
-15 oC
SO2 .
NaOH
H2O

SO3H

CH3

SO3H

, ,
.

, C12-C15.
,
:
CH3(CH2)n
CH3(CH2)m

SO3Na

CH

, ,

-, -:
Cl

98%- H2SO4
80-100 oC

Cl

SO3H

60%- 80-100

-:
O2N
O2N

60%- SO3
80-100 oC

SO3H (65%)

-, , 20%-
4--2-:

1106

1107

HO3S
H3C

NO2

20%- SO3

H3C

60 oC

NO2 (80%)

I , 90-100%-

NH3

( )
,

180-200 ,

-.
, :
NH2

NHSO3H

NH3HSO4

180-200 oC

-H2O

SO3H

, 2-, 2 1--8-.
:
SO3H

HO3S

SO3H

OH

OH

OH
HO3S

1107

HO3S

1108

OH NH2
SO3H HO3S
HO3S

SO3H

NH2

H2N
OH

OH -

.

.

.
S- ,
:
C6H5 + H2NCNH2

H2N=C-NH2 Cl

S
ArSO3Na + H2N=C-NH2
Cl

S
2-

CH2C6H5

ArSO3 H2N=C-NH2 + NaCl

SCH2C6H5

SCH2C6H5

13.7.6..
,

, , .
,
.

()

:
ArSO3Na + SOCl2

ArSO 2Cl
10-20 oC; 10

4-5 .

:

1108

1109

CH3

SO2Cl + ROH

H2N

0...-5 oC

CH3

SO3R + C2H5NHCl

H2N

SO2Cl + NH3

SO2NH2

ROTs, F3SO3R

:
Nu + ROTs

RNu +

OTs

Nu = Hal ,CN , NO2 .

ROTf

CH3COOH

ROCCH3 + TfOH
O

:
ROH

TsCl
C5H5N

ROTs

LiAlH4

RH

ArSO3H
ArSH. .

,
0 o :
CH3
Na2CO3

SO2Cl + Zn

CH3

2-
90 oC

SO2Na

ArSO2Cl

HCl

CH3

CH3

Zn + H2SO4
0 oC

O
O

2Zn

O
OH

ArSH

, :

1109

1110

OH
OH

96%-

NO2

SO3H

H2SO4

HNO3

O2N

HO3S

O3S

O + Br2
Br

NO2
Br

Br

OH

H2O
0 oC

Br
Br

Br

SO3H

1110

Br
Br

1111

14.

14.1.
14.2.
14.3. .
14.3.1. -, -
14.3.1..
14.3.1..
14.3.1..
14.3.1.. .
-
14.3.2. (,
. )
14.3.3.
14.3.3..
14.3.3..
14.3.3..
14.4.
14.4.1.

14.4.2.
14.4.2..
14.4.2.. -
14.4.2.. .
14.5.
14.5.1.

14.5.2.

14.5.3.
14.5.4.

14.5.5.
14.5.6.
14.6.
14.6.1.

14.6.2.

14.6.3.
14.6.4.
14.6.5.

1111

1112

14.1

, , ,

Cl, Br, H, NO,

NO2, , CH3, Ar3C,
ArO ..
,
CH3 CH3 CH3
,

.
, ,
,
. CH3 CH3 -
(, ) ,
CH3,
. ,
C C,
(. . 4.6. . 4, .1).
, - C C
:
, :
CH3-CH3
CH3-CH3

+
CH3 .. + CH3

CH3 + CH3

, ,
. NaCl
. ,

, NaCl Na+ Cl-,

.
,

1112

1113

NaCl,
.
.

). ,
, ,
,
.
. ,

.
, , ,

.

,
, .
- -. ,

:
H
+R
R

( -)

1113

R'

R + R'H

1114

-,
(),
-. -
, ,
sp2- .

CH2

14.2.
-, - - ,
,
, (-).
,

, (-

):
.
H

F
F

()

HO

H
H

()

,
,
.
,

.
.

H
H

()

()

1114

1115

( , . . 3,
.1).

( )

, - -
XCH2CR2, :
() - ():
X

.
R
H

H
R

R
H

H
R

-, (X = CH3, R =
H) -, - (R =
X = CH3) ,
X R.
R3MCH2CH2 (M = Si, Ge, Sn)

pd-

:
.

R3 M
C

R3 M
C

R3 M

-
. , HBr
Br2

()-

.
,
(. 5, .1):

1115

1116
Br
.

C + Br

Br
.

Br
C

(-)

Br

Br

-, -
(),
:
H
H

. Cl
C

H
H

),
.
- ,
d-
.

, :
.

CH3

00

CH3
H

H
H

,
C C = C.
-, -:
.

.
C

-
()

.
14.1
14.1

1116

1117

R3Si .

R3Ge .

()

()

(
p-

R2N..

,

sp2-)

.. ..

R2 N O
.. .

.. ..

R2C N O
.. .

C=N-O

14.3. .
() ,

, .

, .
, ,

,
, ,

1117

1118

,
(,
C H), , ..
, .
.
1. - :
) :
.

R + O2

R-O-O

Ph + R

Ph-R

Ph + Ph

Ph-Ph

Ph3Si + Ph3Si

( )

Ph3Si-SiPh3

( )

) :

CH3CH2 + CH3CH2

CH2 CH2

CH2 = CH2
CH3 - CH3

CH2 CH3

2(CH3)2CHS

(CH3)2CHSH + (CH3)2C=S

CH3CH2 + CH3CH2CH2

CH3CH3 + CH3CH = CH2 (-)

2. -:
) :
.

CF3 + CH4

Cl + CH4

CF3H + CH3

HCl + CH3

) :
.

R + CHX = CHY

RCHX-CHY

) (. 5, .1)
) (. 14.5)
) :
.

Ar + CuCl2

ArCl + CuCl

1118

1119

14.3.1. -, -
14.3.1.. ,

1900 .
. , Ph3C
CPh3 (

).

- Ph3CCl Na

.


(C6H5C-O-O-C(C6H5)3. CO2 N2
(C6H5)3CCl ,
,
.
, ;
,
,
. (. ,
1909),
:
(C6H5)3CCl + Ag

800

AgCl + (C6H5)3C

(C6H5)3CC(C6H5)3,

(C6H5)3C,
:
.

(C6H5)3C + O2

1119

(C6H5)3C-O-O-C(C6H5)3

1120

*.

, .
,
, - ,
- ,

-2,5,

1--4

2(C6H5)3C

(C6H5)3C
H

C(C6H5)2

100 17%, 2 3%.
-, -

(. 14.2).
14.2

0,2 20

Ar Ar3C

Ar Ar3C

,%

,%

-CH3C6H4

87

-PhC6H4

100

40

-PhC6H4

60

16

-PhC6H4

100

CH3C6H4

-CH3C6H4

-FC6H4

7.5

Ar3C

-ClC6H4

12

(-

75

CH3C6H4)2

-.

1120

1121
CPh

-BrC6H4

17

14

PhC6H4CP
h2

, . 14.2, ,

, .
, ,
40 45,

1,48, ,
(1,53). C C C (118)
sp2- .

-.

-, 50% (C6H5)3C
. - -
, . - -
,

,
.
.
,
-(4-)-
30,

-(2,6-)

50.
,
-, - -,
-.

. -
1121

1122

(,
) -
. , - ,
. , -() ,
-C6H5-C6H4(C6H5)2C - .
-
. 3%- --
60%, ----

(C6Cl5)3C, . (1971).
, , NaOH
,

300.

60,
.
- .
(C6Cl5)3C ,

. ,

9 (I) 9- (II) :
.

.
H 3C

CH3

CH3
(I)

(II)

1122

1123

.
9--
9- ,
.
, (III):

.
C

(III)

.
1932 .,
, ,
.
(III) - 25
, .
14.3.1..
Ar2CH Ar2CR ,
.

(C6H5)2CH ,

. -

:
.

(C6H5)2CHBr + (C2H5)3Si

(C6H5)2CH + (C6H5)3SiBr

Ar2CH . ,

1123

1124

- (IV),
,
(V) :
C(CH3)3

(CH3)3C

C(CH3)3

C(CH3)3

(CH3)3C

C(CH3)3

H C

C(CH3)3
(CH3)3C

C(CH3)3

(CH3)3C

(IV)

(V)

Cl

Cl

C
Cl
Cl Cl

Cl

Cl

Cl

R
Cl

R R1 = Cl C6Cl5.
Ar2CH
.
14.3.1..
C6H5CH2

.
,--- (VI)
.
-
,

:
C(CH3)3
C

C(CH3)3

C(CH3)3
O
C O C
C(CH3)3

1124

Na / K

C(CH3)3
C.
C(CH3)3

1125

C6Cl5CCl2.

:
.

2C6H5CCl3 + 2Cu

2C6H5CCl2 + Cu2Cl2

.
14.3.1..
.
-

. 1900 .:
.

Ar3CHal + M
Ar3C + MHal
M = Ag, Hg, Zn

.
, ,
, , ,
, . Ar3CCl

Ar3CBr

, -, -,
.
,

(Ar3C+),

. (1923).

(II), (II), (II). -
,

:
Ar3C-OH

H2SO4

+ VCl2

Ar3C

1125

Ar3C + V

3+

2,2,2,6,66-

1126

:
O-CH3
3

O-CH3

O-CH3

C-OH

10%- H2SO4
H2O -

O-CH3

CrIISO4
H2O -

O-CH3

O-CH3

K3Fe(CN)6,
AgNO3, , :
Ar3C:

Ar3CH

[O]

Ar3C

(. , 1924):

.
2Ar3C K+ + (CH3)2C C(CH3)2
2Ar3C + (CH3)2C C(CH3)2 +2 KBr

Br Br

Ar2CH Ar2CR , :

.
2 Ar2C:K+ + (CH3)2C C(CH3)2
2Ar2CR + (CH3)2C C(CH3)2 +2 KBr

R
Br Br

:
Ar2C O-CH3 + 2K
R

- +
Ar2C : K + CH3OK
R

(Z-C6H4)2CH
. :
(ZC6H4)2CHBr + Ag

(ZC6H4)2CH + AgBr

1126

(94%)

1127

(C6H5)3CH + SO2Cl2 + S2Cl2

(C6Cl5)3CH + KOH
Cl

Cl

H
C
Cl
Cl Cl

I2

- O2
(C6Cl5)3C:

Z' + NaOH

(C6Cl5)3C.

N2
-

Cl

Cl

Cl

Cl

C
Cl
Cl Cl

Cl

C
Cl
Cl Cl

Cl
Z'
Cl

Z Z' = Cl, C6Cl5

Z'
Cl

Cl

Cl

Cl

Cl

Cl

(82%)

Cl

(C6H5)3CH

SO2Cl2

Cl

Cl

AlCl3

:
Ar3C

2 Ar3C.

Ar2CH

2 Ar2CH.

CAr2

CHAr

. (C6H5)2CH
.

. , ,

-(2,6-)

-(2,6-

) - 25 0,35 2%
, -(2--) 0,6%.
, , (CH3)2CH (CH3)3C,
70 100%.
1127

1128

, , -- [(CH3)3C]3C
-- [(CH3)3C]2CH, .

2 ArCH2

ArCH2CH2Ar

,
. ,
:

(C6H5)3C.

Ph

(C6H5)3CH +

Ph

9-

,
:
Cl

Cl

Cl

(C6Cl5)3C.

Cl

Cl
Cl
Cl

Cl
Cl
Cl

Cl

Cl
Cl

, .

,

VII, :

1128

1129

H3 C

Ag

CCl

H 3C

CH3

H3 C

CH + H2C

CH3

(VII)

:
.

2 Ar2CCH3

Ar2C=CH2 + Ar2CHCH3

, , HCl, .
,
Fe (III), Au (III), Hg (II) ..
. - Ar3C

, :
(C6Cl5)3C +

- eE1/2 = + 1,17 B

(C6Cl5)3C.

+ eE1/2 = - 0,85 B

(C6Cl5)3C:

,
:
Ar3C. + O2

Ar3C O O CAr3

. .
, ,
,
.
, .
,

1129

1130

(C6H5)3C-O-O .

(C6H5)3C. + O2
2 (C6H5)3C-O-O.

(C6H5)3C-O-O-O-O-C(C6H5)3

(C6H5)3C-O-O. + (C6H5)3C.

(C6H5)3C-O-O-C(C6H5)3

(C6H5)3C-O-O-C(C6H5)3

, Ar2CH,
Ar2CO, Ar2CHOH
Ar2CHOCHAr2. (II)

.

(IV)

:
2 (C6H5)3C. + 2 NO2

(C6H5)3C-NO2 + (C6H5)3C-O-N=O

,
(IV). -
:
C6H5

(C6H5)3C. + C6H5.

C(C6H5)2

100:
.

Ar3C + C6H5CH3

Ar3CH + C6H5CH2

Ar3C + C6H5CH2

Ar3CCH2C6H5

. .

1,4-
:
2 (C6H5)3C + CH2 C CH CH2
CH3
(C6H5)3C CH2 C CH CH2 C(C6H5)3
CH3

1130

1131

14.3.2.
(, , )
.
(1911 1915), Ar2N NAr2

Ar2N NAr2

2 Ar2N

-
(90 100), C C-
( ),

,
:

(C6H5)2N-N(C6H5)2

90 - 1000C

C6H5
N

2 (C6H5)2N

(C6H5)NH +

N
C6H5

. ,
,
0 20:
CH3-O

O-CH3

CH3-O
200C

N N
CH3-O

O-CH3

H3 C
H3 C

N N

CH3
CH3

1131

N.

2
CH3-O

H3 C
00C

CH3

2
N
.

1132

, -

(II),

:
.

Ar2N + (C6H5)3C.

Ar2N + NO

Ar2B-C(C6H5)3
Ar2N-N=O

20
(3%), .

, .
NO, (C6H5)3C
.
20% -(-)
. -
,

,
:

Ar2N

NAr2

(IV) .
,
,
1,3,6,8----9- (VIII),
:
(CH3)3C

C(CH3)3
N
H
C(CH3)3

1) BuLi; C6H6

(CH3)3C

2) I2

C(CH3)3
N
.

C(CH3)3

C(CH3)3

C(CH3)3
(VIII)

1132

1133

, ;
:
Ar
Ar

N
+
K

Ar

Ar

+ Cl2

Ar

Ar

Ar Ar

Ar

Ar

N
N
.

Ar

Ar

Ar

Ar
Ar

Ar

Ar2N

NAr.

(. 14.3.3)
.
1,1-2-

(),

. 1922 .
:
O 2N

O 2N
NO2

(C6H5)2N NH

PbO2
CHCl3

(C6H5)2N N

O 2N

NO2

O 2N

.
1,1- -
:
O2N
Ar2NNH2 + Cl

O2N
NO2

O2N

Ar2N N
H

NO2

O2N

.
,
.
:

1133

1134

1)

;
2) ,
;
3) .
, ,
, ,

.

(C6H5)2N-N-C6H5 .
, 55
, 0 .
,

.
:
O2 N
(C6H5)2N N

NO2

(C6H5)2N N

O2 N

O2N

R2N-NR

R2N-NH
().

,

1134

1135
NO2

NO2

(C6H5)3C. + O2N

N N(C6H5)2

O2 N

C(C6H5)3

N N
H
C 6 H5
NO2

NO2

(IV),
NO:
O2 N

O2 N

Ph2N N

O2 N

NO2 + NO2

C6H5

O2 N

NO2

N N
H
O2 N

.
:
RSH +
2 RS

RSSR

RS +

RS + -H
O2 N
SR
Ph2N N

NO2

O2 N

, (. 23, .3),
-.
(. 23)

2,4,6---

:
OH

O
+ -H

-:

1135

1136

..

+.

OH

OH

O2 N
-..
Ph2N N

NO2

O2 N

O
+ -H

,
, 1,7
- :
+ +e
()
- e-

()

- e-

()

- 0,12

0,5

+ e-

+ e-

- e-

().

- 1,71

+ e-

- e-

()=

- 2,03

N,N---

-,

.+

..

N(CH3)2

N(CH3)2
()- +

() +

N(CH3)2

N(CH3)2

, , Fe2+, Sn2+,
Cr2+ .

1136

1137

, 1,2,4,5-:
R
Ar N
N

R
Ar
Ar
N Ar
N
N N
N
N
N
Ar N
Ar
R
R

R
N
N Ar
Ar

1,2,4,5-

N-.

,
:
H
Ar N
N

N Ar
N

CH3I

Ar

Ar

CH3
N
N

N Ar
N

Ar N
N

Ar

N Ar O2
Ar N
NH K Fe(CN)
N
3

Ar

N Ar
N.

Ar

:
Ar N HN Ar
N
N
2

Ar
N N
N.
2 N
Ar

PbO2

Ar

Ar

:
Ar2N NH2 + HC(OEt)3

Et2O.BF3

Ar2N N CH NH NAr2

PbO2
C6H6

Ar2N N CH

,
, ,
,
.
14.3.3.

1137

NAr2

1138

R2N-O,
.

(KO3S)2N-O, 1845 .

NO, ,
.

,
:

..

R
R N

.
O

:
:

R
R N

..
O

:
:

[(CH3)3C]2N-O,
, 33 /.

.
.
,
, :

2pz

2pz
2py

N O

*-,

2pz- .
N O

1138

1139

1,26 1,28, ..
N O N = O .
260,

80
(IX):
O

+ R
R +
N
N
R
R
O

(IX)

. ,
, ,
. ,
,
:
R'
2 RCH2 N O

R'
+ R'
RCH2 N OH + RCH N
O

-- , t-Bu2N-O
100

--

,
. ,
,

-()-

(CF3)2N-O, .

--

1139

1140
H

..

..

N C(CH3)3
O.

(CH3)3C N

N C(CH3)3
O

C6 H 5
+

C6H5NHC(CH3)3 + O

N C(CH3)3
O

N-- N----N-.

. -
-

--(--

)
. --
-
:
..

2 R2CH

N C(CH3)3
O.

..

R 2C

N C(CH3)3 + R2CH
O

N C(CH3)3
OH

.
14.3.3..

:
R2N OH

[O]

R2N O.

, PbO2, Ag2O, MnO2, H2O2,

1140

1141

.
(. , 1914 1922)

:
1

Ar N=O + Ar MgBr

Ar

..

Ar

..

N OMgBr
2
Ar

Ag2O

N OH
Ar
; 0 - (-10)0C
2
Ar

H2O

..

N O.
2
Ar

:
R
R C NH-OH R C O
+
R C NH-OH
H
R

OH
N R

R
R
R
R

PbO2

N R
OH

R
R
R
R

O
+
N R

..

N
O.

, :
H3C

H3C

CH3

1) RMgX

N O

H3C

CH3

1) RMgX

N O

2) O2

2) O2

CH3

..

N O.
RR

N- :
PhMgX

N+
O

Ph
..
N
Ph
OMgX

Ph

O2

..

N
O.

Ph
Ph

, -,

.
,

(-

) .
,
1141

1142

, - .
:
R
R'

NH + H2O2

Na2WO4
H2O

R'

R .. .
N O
R'

NHOH

R R' - -Alk

- . --

2--2-
:
CH3
..
Na
2 H3C C CH3
(CH3)3C N C(CH3)3

NO2
O.

--

-.
(
), :
H3 C

. O N:
H3 C

O.
N
.. C(CH3)3

O.
(CH3)3C N
..

CH3
CH3

CH3

:N O.

CH3
CH3

CH3

H3 C
H3 C

..

N
O.

N CH

HC N

CH3
CH3

H3 C
H 3C

..

N
O.

CH3
CH3

14.3.3..
.

,
.
,
:

1142

1143

Pt

R2N-OH

..

Ni

R2N-O. + H2

R2NH + H2O

.

:

..

2 R2N-O. + 3 HCOOH

2 R2NH-OH + 2 HCOO + CO2

(II)
HCl
:

..

+
2 R2NH2Cl + 3 SnCl4 + H2O

2 R2N-O. + 3 SnCl2 + 8 HCl

.
, --,

(. . 23, .3):
O
OH

..

+ (KO S) N-O.
3

CH3

CH3COOK
CH3OH - H2O

(82%)

+ HON(SO3K)2
CH3

(. 23).

, , 9,10-

20
:
H

..

+ 2 R2N-O.
H

200C
C6H6

+ 2 R2NOH

:
R ..
N O.
R

1143

- e-

R
R

N O

1144

,
, , .:
CH3
CH3

CH3
CH3

:N O. + Br2
CH
CH3 3

- 250C
CCl4

N O

Br3

(99%)

CH
CH3 3

-:
..

R2N-O. + Ph3C X
+

R2N =O X + Ph3C.

Ph3C. + O2

Ph3C-O-O-CPh3

.
,
, ,
,
.
. ,
, --
- :

..

t-Bu2N-O. +

t-Bu2N+=O + -

,
(C6H5)3C:
..

2 Ph2N-O.+ 2 Ph3C.

Ph
..
Ph2N O C
Ph

..

CPh3 + Ph2N-OH

(II)
.
NO2 -().
1144

1145

2,2,6,6-4--1-, :
OH
H3C
H3C

NHCH2CH2OH
H3C
H3C

..

N
O.

CH3
CH3

2) NaBH3CN
CH3OH

H3C
H3C

..

N
O.

CH3
CH3

NaBH4

1) HOCH2CH2NH2

..

N
O.

CH3OH

CH3
CH3
NOH

NH2OH

H3C
H3C

..

CH3
CH3

N
O.

,
.
2,2,6,6-4--1- :
OH

O C
O

H3C
H3C

..

N
O.

CH3 + R C
Cl
CH3

C5H5N
C6H6

H3C
H3C

OTs
H3C
H3C

..

N
O.

..

N
O.

O
R
CH3
CH3

Nu
CH3
CH3

+ Nu :

H3C
H3C

1145

..

N
O.

CH3 + TsO
CH3

1146

,
.

,
, (.
14.4.2).

. -,
. -
, , , ..

,
.

.
14.3.3..
ArO,
- .

.
23 (.3), .
14.4.
14.4.1.

. ,

1146

1147

, ,

:
O
O
H3C C O O C CH3
R N N R

O
2 CH3 C O.

1000C

2 CH3 + 2 CO2

2 R + N2

, , ,
, :

R + C6H5 C O O C C6H5
O
O

C6H5 C

O
+ C6H5 C
OR
O.

C6H5 + CO2

,
:
(CH3)3C O O H + Fe

2+

(CH3)3C O. + Fe + OH
3+

, :
+

Ph3C + V

2+

3+

Ph3C + V

30
50 /.
100 150 .
, O O
40 /,
80 100:
(CH3)3C O O C(CH3)3

800C

2 (CH3)3C O.

- 60 11
, 100 200 , 150 1 , 180
; - -,
, :
1147

1148
CH3
H3C C O.
CH3

O
.
CH3 + CH3 C CH3

60 100, CO2
. , -,
- .
90 2 , 100
0,5 .
,
,
.
-
. ,
,
(,
..),

.

,

.

, , (. ),
.

.
,

100,

:
CH3
CH3
H3C C N N C CH3
CN
CN

1148

800C

2 (CH3)2CCN + N2

1149

60, 80 100
17, 2 0,1 . ,
400, , ,

.
.

.

.
.
, , ,

,

:
.

X + CH3CH2 O O CH2CH3

HX + CH3CH O O CH2CH3
CH3CHO + CH3CH2O.

CH3CH O O CH2CH3

.
X ,
.
,

,
. -
,
:

1149

1150

t0

(CH3)3C O O C(CH3)3

2 (CH3)3C O.

(CH3)3C O. + R2CHOH

(CH3)3C OH + R2C OH

R2C O + (CH3)3COH + (CH3)3C O. ..

R2C OH + (CH3)3C O O C(CH3)3

,
.

.

, , , , , ,
.

,
(Cu+, Cu2+; Fe2+, Fe3+; Co2+, Co3+; Ce3+, Ce4+ ..).


(. , 1894).

:
2+

Fe + H2O2
3+
Fe + H2O2
2+
.
Fe + HO
3+
.
Fe + HOO
.
2+
Fe + HOO
.
H2O2 + HO
H2O2 + O2.

3+

Fe + HO + HO
2+
+
.
Fe + HO2 + H
3+
Fe + HO
2+
+
Fe + H H + O2.
3+
Fe + HOO
.
H2O + HOO
.
O2 + HO + HO

(. 14.5.5).
Fe (II), Cu
(I), Co (II), Ti (III)
, :

1150

1151

II

III

(CH3)3C O OH + Fe

(CH3)3C O + OH + Fe

CH3
III
C6H5 C O OH + Ti
CH3

CH3
IV
C6H5 C O. + OH + Ti
CH3

,
(I):
O
C6H5 C

+ Cu
O O C(CH3)3

II

C6H5COO + (CH3)3C O + Cu

, :
O
+ C6 H5 C

Cu2Br2

OOC(CH3)3

800C

+ (CH3)3C-OH

O C
C 6 H5

(80%)

:
C6H5 C

O
.
II
C6H5 C + (CH3)3C-O + Cu
O

+ Cu

OOC(CH3)3

+ (CH3)3C-O

II
. + Cu

. + (CH3)3COH
I

+ Cu

+ C6H5COO

O
O C C6H5

--

, (II).

.
, .
,

1151

1152

:
(CH3)3C CH2 C

O
O O C

O
.
II
(CH3)3C CH2 + (CH3)3CCH2C + CO2 + Cu
O

+ Cu

CH2-C(CH3)3

II

(CH3)3C CH2 + Cu

(CH3)2C CH2CH3

(CH3)3C CH2 + Cu

-H

(CH3)3C CH2 + Cu

(CH3)2C=CHCH3

Nu:

(CH3)2C CH2CH3
Nu

, ,
, -, -
-, , ,
, ,
:
I

(RCOO)2 + Cu

II

II

RCOO + R + CO2 + Cu

R + Cu + X

RX + Cu

- (RCOO-)
(RCOO),
CO2 (R).

, , Mn (III), Ce (IV) Pb
(IV). R R+
( ),
.
,
.
,
,
:

1152

1153

COOH

OAc

Pb(OAc)4

AcOH

CH2OAc + CH2=CHCH2CH2OAc

(52%)
OTs

(44%)

(4%)

OAc
AcOH

CH2OAc + CH2=CHCH2CH2OAc

(47%)

(48%)

(5%)

,
.

-
( , 1965):
Pb(OAC)4, LiCl

CH3(CH2)3COOH

C6H6, 800C
Pb(OAC)4, LiBr

(CH3)3C-CH2COOH

CH3(CH2)3Cl + CO2
(71%)

C6H6, 800C

(CH3)3CCH2Br + CO2
(76%)

:
Hal
IV
RCOO Pb

Hal
III
.
R + CO2 + Pb

IV

III

R + Hal Pb

III

Pb + RCOO

R-Hal + Pb

II

R + CO2 + Pb

..

Pb (IV)
-, CO2 Pb (III). -
Pb (IV)
Pb (III) -. -

.

, -.

1153

1154

,
.
, , - (II)
,

(II) :
.

(CH3)3CCH2

CuCl2

(CH3)3CCH2

(CH3)3CCH2Cl
+

(CH3)3CCH2

OAc

(CH3)2CCH2CH3

(CH3)2CCH2CH3 + (CH3)2C=CHCH3 + CH3CH2C=CH2

OAc
CH3

,

.
14.4.2.

14.4.2..

().

. ,
,

,
,
.
,
.
(KSO3)2NO.

1154

1155

,
,

, 0,2
. 108

M.

g-,

. g-
. g
.

(1H,
17

13

C,

14

N,

O ..).

-
1:3:3:1. 1:1:1.
, .

13

, s-,
p-. ,
(-),
-.
14.4.2.. -
,
, ,
,
.

1155

1156

- (
). - ,

,
, :
.

R + - ()

(R-)

(, 2--2-; X) (N---; XI),

,
(. 14.3.3):
t-Bu ..
.
N O
R
R
PhCH ..
.
N O
t- Bu

R + t-BuN=O
(X)

R + PhCH=N

O
Bu -t

(XI)

,
R.
14.4.2.. . .
, ,

( )
.
, .

:
.

, .

1156

1157

-,

,
, ..
.
().
.
, ,
.
,
.

. R1 R2

,
. R1 R2
() ,
,
(, ,
):
1

R.

R.

R. + R .
1

R R , R R
R R ( )
1
2
R H + (R )-H ()
1
2
R H + R H ( )

R1 R2 ,
R1 R2 ,
.
, ,
(,
)

1157

1158

),
, , -
.

, ,
:
1

R
T

( S).
( T),

, (B0)

g- .
R1 R2 , g-
, (g1 g2), (S T) g-
.
(a)
(m). , (S T)-
:
( g 1 g 2 ) B + ( a1 m1 a 2 m2 )

,

, g-.

R1 R2.
, R1 = CH3, R2

1158

1159

(.. a2m2 = 0). (a1 < 0), ,

. ,
, ..
, ,

.

.

,

.

CH2CCl3,

:
500C

CH3C O O CCCl3
CCl4 (+I2)
O
O

H3C

. .

CCl3

I2

CH3I + CCl3I

CH3CCl3
( )

CH3I .
,
, ,
, , .
(. . 4, .1)

14.5.
,
:
.

Ar-X + R

Ar-R + [X ]

, .. X = H.
(R = Ar), .

1159

1160

, ,
.

14.5.1.

-),

- SE- (. 13) SNAr- (. 15) :

H

R H
+ R.

-
(XII)

(XII)

, ,
. ,

(XIII)

(1)

(2)

(3)

1160

1161

(1)
Ph

Ph

Ph

+ Ph-Ph

(2)

(XIII)

H
H

H
Ph

Ph

Ph

(3)

+R

Ph Ph + RH

(4)

- e-

Ph Ph + H

(PhCOO)2,

PhCOO,

:
Ph

+ (PhCOO)2

Ph Ph + PhCOOH + PhCOO

- CO2

+ C6H6

Ph

NaOH

.
,

, ..
.
:

1161

1162
PhNH2 + C6H11ONO
Ph NH N=O + C5H11OH
PhNH N=O
PhN=N-OH
+
PhN=N-OH
PhN N + OH
PhN=N OH + OH
PhN=N-O + H2O
+
PhN N + PhN=N-O
(PhN=N)2O
.
.
(PhN=N)2O
Ph + N2 + PhN=N-O
Ph

Ph + PhH

.
PhN=N-O

Ph Ph + PhN=N-OH ..

PhN2

Ph
Ph Ph + H

+ N2 + Ph ..

NaOH.
14.5.2.

.
,
, -, (
) , -,
- -,
, (. 14.3).
14.3
,
PhX + (PhCOO)2 80
PhX

, %

1162

1163

1
)

PhN

O2

,
9
4

PhI

PhPr

PhCl

2
,

PhN=N-OH
1163

1164
2
0
PhF

PhC

H3

,
5
8

PhC(

CH3)

0
9

PhPh

2
,
9
4

PhO

CH3

,
7
1

, ,
- . -, -
,
(. . 13). ,
,

- -:

1164

1165
Ph

Ph

Ph

Ph

+. OMe

:OMe

- N
. N
O
O
O
O

. 14.3 (. . 13)
.
, - f
, f, ,
. ,
f . .
14.5.3.

- . . 14.4

80 ,
-

, II ,
- (,
- -).
14.4
C6H5CCl3
RC6H4
, %

C6H5

60

40

-ClC6H4

83

17

100

O2NC6H4

-.
,
1165

1166

,
, :
O

N
+

80.
. 14.5, - -
-

.
14.5

, %

C6H5

62,5

9,8

27,7

C6H5

59,0

13,8

27,2

NO2

ClC6
57,7

13,2

29,1

C6H5

50,1

31,6

18,3

59,6

24,2

16,2

C6H5

49,3

33,3

17,4

60,5

25,1

14,4

20,8

53,4

25,8

C6H5
NO2

H4
C6H5

NO2

BrC6
H4

C6H5
Cl
C6H5
Cl

O2NC

6H4

C6H5
Br
C6H5
Br

O2NC

6H4

C6H5

C6F5

NO2

1166

1167

14.5.4.

,
(II) (. 14.6).
14.6
(PhCOO)2

, %

40

85

(PhCOO)2Cu

88

(PhCOO)3Fe

90

, :
Ph

+ O2

Ph Ph + HOO

,
(. 14.5.1).
(II) :
Ph

Ph
2+

+ Cu

H
+

+ Cu

Ph Ph + H
+

II

Cu + (PhCOO)2

PhCOOCu + PhCOO

14.5.5.

,
. ,
, -/-

1167

1168

, ,
,

.
,

9 (10).

, ,
, , , , ,
.
,
.
,
- -
:
R
RCOOH
+

2-

+
R

S2O8 /Ag /H

(I)
:
2-

S2O8 + 2 Ag

2+

Ag + RCOOH

2+

2 Ag + 2 SO4

2-

R + CO2 + Ag

(- -):

1168

1169

..

N
H

..

N
H

N
H

R
R

H
+
. NH

-e+

N
H

-H

H
-e-

-H

N+
H

N
H

S2O82-/Ag+.
,

- ,
.

.
14.5.6.

,
.

-. - -
.

.

FeSO4:
2+

Fe + H2O2

3+

Fe + OH + HO

(XIV),

, :

1169

1170
H

OH

+ OH

OH

Ph Ph + 2 H2O

HO

(XIV)

(XIV) ,
(II), (III) :
H

OH

+ Cu

H
2+

OH
+

+ Cu

Ph OH + H

, ..
, ,
-
(. 14.7).
14.7

, %

PhX

6,35

85

11

55

15

30

PhF

37

18

45

PhCl

0,55

42

29

29

PhN

0,14

24

36

46

(
-1)

PhOC
H3
PhCH
3

O2

14.6.

C=C, CC, C=O, N=O .
,
1170

1171

.
R,
, (Cl, Br),

(-):
.

R + CHX=CHY

RCHX CHY
-

-
, ( ),

-).

-
, , .

,
:
.

RCHX CHY

X + RCH=CHY

( )

, -
X,
C X, .. .
,

, :
, .
:

-

R COO

-e-

R COO

R + CO2
R R

( RCOO 10-9 10-10 ).

-

1171

1172
Me
i- Pr C O Cl
Et

Me
i- Pr C O.
Et

800C
.
- Cl
CCl4

(<0,5%)

(95%)

CCl4 (3%)

Me C Et + i- PrCl + CCl3
O

CCl4

Et C Pr -i + MeCl + CCl3
O

Me C Pr -i + EtCl + CCl3
O

R + CO

R C

.
R C

CCl4

R C Cl + CCl3
O

, .. R
. ()-
:
I2

2I

Ph
H C

Ph

Ph
.
+I
C
C
H
H
-
Ph
H C

C
H

Ph

H
C

+I
Ph
H
-
C

Ph

Ph

RZ,
:
.

RCHX CHY + RZ

RCHX CHYZ + R

RZ
, 1:1- -

1172

1173

. :
.

CCl3Br
CCl3 + Br ()
.
.
CCl3 + RCH=CH2
RCHCH2CCl3
.
.
RCHCH2CCl3 CCl3Br
RCHBrCH2CCl3 + CCl3

,
, ,
R(CHXCHY)nZ, n
2 10:

RCHX CHY + CHX=CHY

RCHX CHY CHX CHY

...

RZ

R(CHXCHY)nZ

,
, :
.

R(CF2CF2)n-1 + CF2=CF2

R(CF2CF2)n

R(CF2CF2)n + RZ

R(CF2CF2)nZ + R

(
, n=103 104);
.
,

:
.

RCHX CHY + R

RCHX RCHY

.
14.6.1.

(H, Cl .)
,

,
, .

1173

1174

CH3 C2H5
, (CF3),

. , CF3
, .
,
.
CF3- , CH3,

, , CH3 , CF3.

14.6.2.

-
.
, 1:1-:
.

RZ + In
R +

()

R + InZ
R C C

.
( )

.
R C C Z+R

.
R C C + RZ
.

R +R

( )

R R

. 1:1-

CCl4,

CCl3Br

,
,

: CX3I > CX3Br > CX3Cl:

1174

1175

CCl3

+ CCl3Br

Br
h

RCH=CH2 + CFCl2Br
CF3CF=CF2 + CF3I

RCHBr CH2CFCl2
CF3CFICF2CF3

(94%)

, :
CH3CH2CH2C

O
+ CH2=CH(CH2)2COCH3
H

C2H5OH + -C3F7CF=CF2

CH3CH2CH2CCH2-CH2(CH2)2COCH3 (70%)
O
- C3F7CHF-CF2CHCH3
OH

-1.
--, --,

,
. , :
2 (CH3)3C O.

(CH3)3C O O C(CH3)3

+ (CH3)3CO
H

N
H

N
H

N
H

+ (CH3)3COH

+ C6H13CH=CH2
N
H

(CH3)3COH

CH2 CHC6H13

N
H

+ (CH3)3CO
(CH2)7CH3

-
, . -. ,
, :
PhC CH + CH3CHO

CH3COCH=CHPh

CH3CHO
h

CH3COCH(Ph)CH2COCH3 + PhCH2CH(COCH3)2

, - , ..
1175

1176

,
, .
,
.
HBr , - ,
(. 5, .1):
H Br

Br

CH3CH=CH2 + Br

CH3CH-CH2Br

CH3CH=CH2Br + HBr

CH3CH2Ch2Br + Br ..

.
(. . 5)
.
Br H = -11 /,
- HBr H = -7 /. ,
. HCl
(H = - 22 /),
(H = +8 /), HI, ,
(H = +7 /),

(H

-24

/).

HBr,
,
.
,
.
F2, Cl2 Br2
.
,
( 5, .1). , -1
:

1176

1177
Cl2

CH3CH2=CH2 h

CH3CH2CHClCH2Cl
(85,5%)

+ CH3CH=ChCH2Cl (7,5%)
+ CH3CHClCH=CH2 (2,5%)
+ CH2ClCH2CH=CH2 (4,5%)

:
R3MH + XCH=CH2

R3MCH2-CH2X

(R = Alk, Ar, Hal)

:
(CH3)3CC CH + HSiCl3

(CH3)3C

SiCl3
C

(39%)
H

CH2=CHCN + HGeCl3

Cl3GeCH2CH2CN
(53%)

CH2=C=CH2 + HSnMe3

Me3SnC(CH3)=CH2 + Me3SnCH2CH=CH2
(37%)

C O,
H, , O H.
-

.
RSH

-,

:
C2H5SH + -BuOCH=CH2

-BuOCH2 CH2SC2H5

RCOSH, -
,

1177

1178
PhSO2Br + CH2=CHBr

PhSO2CH2CH2Br

NaHSO3 + RCF=CF2

(73%; R=-C5H11)

RCHF CF2SO3Na
h

RSSR + CH3C CH

(67%)

H3C

SR
C

RS

H3C

H
C

RS

SR

(64%)

(16%)
(R=-Bu)

14.6.3.

: - -:
.

RCH2 CHX (-)

R + CH2=CHX

RCHX CH2

( -)

1:1-:
.

RCH2 CHX + RZ

RCH2 CHXZ + R

RCHX CH2 + RZ

RCHX CH2Z + R

,
. 1,1-

R ,
X Y XCH=CH2 XYC=CH2. 1,2-
, , .
. . 14.8
-, -

1,1-

.
14.8

(:)
150

CH2=CHF

CH2=CF2

CHF=CF2

CF3

1 : 0,09

1 : 0,03

1 : 0,50

CHF2

1 : 0,19

1 : 0,15

1 : 0,95

1178

1179

CH2F

1 : 0,30

1 : 0,44

1 : 2,04

1 : 0,20

1 : 2,10

CH3

CH2-
,
. CF3
CHF-, CH3 -

CF2-.

.
, .

.

, - CF2=CHF
, - CH2=CHF.
:

CHF=CH2

.CH

CH2=CHF

0,44 - 0,49

0,46 - 0,51

.
H

0,37 0,27

0,47 0,30

C=C-
() ,

,
CHF=CF2,
1179

1180

CHF=CF2, ,
CH2=CHF, . (
).
,
,
.
CNDO/2
- - , -
*-. , -
C, *- - .
,
- - ( ),
- (. . 14.8).
CF3. ,
CH3, ..
, , CHF=CF2
CH2=CHF.

..

,

- .
CF3, CHF2, CH2F, CH3
,
- .
- ,
(CH3)2P, H2P, (CF3)2P ,
1,1- .

.
,
,

1180

1181

(.

5)

, -
,
:

..

..

X-CH=CH2 + E

{X-CH-CH2E

X=CH-CH2E}

:
..

+.

.. .

X-CH=CH2 + R

..X-CH-CH2R}

{X-CH-CH2R

,
.

, , ,
.
14.6.4.

1,2-

. , CH3S - -2 - -.
HBr HBr

(-()-

):
H3C

CH3
+ DBr
C
C
H
H
--2

Br

- 700C

CH3
H

C
H3C C
H
D
- (95%)

(XV)
C C-.
d- (
C Br- p d
-; . 14.2):

1181

1182
Br

.
H3C
H

H
CH3

(XV)

.
, ,
-
, :
Br
+ HBr

Br

Br

-1,2- (~100%)

14.6.5.

CH2=CH(CH2)nCH2
.

:
.
(CH2)n CH2

(CH2)n

CH2

CH2
(CH2)n

-3--1- ( )

-4--1-

.
-5--1- CH2=CH(CH2)3CH2,

1182

1183

RH

COO

H 3C
(>94%)

.
Bu3Sn

Br

P(OEt)3

RH

SH

(<6%)

,
.
, -5-1-
.
,
:

,

(., , . 26, .3).

-5--1-

. , -,
- (.
14.6.3), ..
( )
.
5- 6- .

1183

1184

, , ,
,

-5--1- ,
5- ,
6-.
1

3
4

.1

.6

6
1

1
3
6

.5
4

4
5

,
. 26 (.3).

1184

1185

15.

15.1.
15.1.1.
15.1.2.
15.1.3.

15.1.4.
15.2. SRN1
15.3. SRN1

15.4.

SNAr
15.4.1. -
15.4.2.
15.4.3.

15.4.4. SNAr
15.4.5.
15.4.6. SNAr

15.5.

15.6. ANRORC
15.7.

SN1
15.8.

1185

1186

:
Z

Nu
-

+ Nu :

+Z

Z () , X
, Nu-: - , (OH-,
OR-, NH2- ..), (R2NH, RNH2,
ROH ..).

, , ,
(-
), ,
(- ).
, SN2, , ,
,

(. . 9, .1), ,

SN2 , C Z ArZ
.

(.

,
.

13),

-:
Z

Z
-

+ Nu :
X

Nu

Nu
-

+Z
X

-,
1186

1187

-.
-.
, X
, , ,
-.
,
( ) (
) Nu:-, ,
(. 15.1),
. , X
(, X = -N+N, NO2, SO2R ..),
- (. 15.4).
,
,
.

(15.1)

,
X, (. 15.4)
.
15.1.

, ,
,
. Nu:-
, -
. -,
- (
-H > -H > -H). (I)

Hal-,
,
(II). :

1187

1188

Hal

Hal

..

H
+ Nu :

+ HNu

- Hal

(I)

(II)

II , ; X = H,
.
.
HNu: ,
:
Nu

.. -

+ Nu :
X

..-

Nu

HNu :

HNu :

Nu

H
H

Nu
-

+ Nu :
X

,
, .
- 15%-

350 400 -
- 2 : 3. -

- -:

1188

1189

CH3 + NaOH
Cl

HOH

CH3 +

350 - 4000C
30

OH

HO

2
Cl

CH3 + NaOH

HOH
350 - 4000C
30

CH3

HO

CH3 +

CH3

HO

- -, 1--2-

1--3-:

Cl + KNH2

NH3 (.)

H 3C

- 330

CH3

H 3C

H2 N

OCH3

NH2

OCH3
Cl
+ KNH2

NH3 (.)

NH2

,
, , ,
OH- NH2-
1942 .
. , -, -, -
, , 2 C6H5F >> C6H5Cl > C5H5Br ~ C6H5I.

2-

1189

1190

C6H5Li
; -

C6H5Li
- LiF

780

Li

OLi
C C6H5

C6H5

Li
C6H5COC6H5

C 6H 5

OH
C C 6H 5

CH3COOH

1953 . .

. , 1
14C, -1-14C -2-14C:

NH3 (.)

+ KNH2

- Cl

..-

Cl

Cl

NH2

..-

NH2

NH3
*-..

+
*

NH2

NH2

(48%)

NH2

(52%)

:
Cl
*

OH
*

4N - NaOH

OH

3400C; H2O

(58%)

(42%)

, (1956)
,

-.

1190

1191

1,4-

-1,4-,

1-:

Br
F

Li

Li - Hg
- LiBr

- LiF

F
OH

HCl
CH3OH

(76%)

(90%)

, :

Br
F

Mg - Hg
; 600C

MgBr
F

(28%)

() ():

Br
F

Li - Hg

(24%)

1191

(3%)

1192

15.1.1.

. .

( , , .).

.
.
, , .
-
. -
- -.

(CH2Cl2)
2-.

CO2 :
+

NH2

N N

C5H11ONO
; - 100C

COOH

h to

COO

+ CO2 + N2

(75%)

,
75%.

-1,1-,
1192

1193

:
NH2
SO2H

HNO2
- H2O; -

100C

200

S O
O
1,1-
OH

HOH

+ SO2 + N2

(88%)

OCH3

CH3OH

CH3OH; - 500C

S O
O

(95%)

1-

:

N
N

N
NH2

Pb(OAc)4
CH2Cl2; -780C

N+
N
-

N
N

+ N2

2-

68%:

1193

1194

I C6H5
COO
Ph

Ph

Ph

Ph

+ C6H5I + CO2

1500C;

Ph
Ph

(68%)
Ph
Ph

, 1973 .
-1,2-
265. 230 :
O
C
C
O

O
O

O
h
-

h
-

2 6 5 0C

2 6 5 0C

15.1.2.

, sp- ,
, 180. ,
, ,
.
. -
, ,
sp2-

sp2-

-, sp2-
.

1194

1195

(4n + 2),
.
, -:

-
1,401

1,387
118o
1,405

118o

123o

1,349

,
.

. , -

sp2-

, , . , ,
- .
-

. , , -
I- (60) > Br- (10) > Cl- (1).
, ,
-.
RS- > (C6H5)3C- > C6H5CC- > > C6H5O- ~ I- > Br- > Cl- > ROH ~ H2O,
.
.

1195

1196

15.1.3.

, ,
.

,
.

, , , H D+
NH2- ,
:
Br
-

NH2 (NH3)

Br

NH2 (NH3)

..Br
D

NH2
H

NH2 (NH3)

- NH2-,

, , :
F

F
D

NH2 (NH3)

()
, ,
, (),
, .
- (
1196

1197

C F) C Br ,
, , ,
-, .
.
, -
, .
:
a)

X
+ NH2

k1

k-1

..-

+ NH3

..-

k2

+X

X=Br k2 >> k-1

X=F k2 << k-1

2,6- .
, , 2--3-
:
Br
H3C

OCH3

NH2 (NH3)

( )

,
( )
, ,
, .
, , :
- ( k1
k2) ()

1197

1198

.
,

.
NH3 -, -
(I II, . ),
( NH2-) III,
IV, V VI:
Hal

(III)

NH2

NH2

+ NH2

NH2

(IV)

X
NH2

NH2

Hal

NH2

NH3

NH3

+ NH2
- X

NH3

NH2
NH2

II

Hal

X
NH2

H 2N

(V)

NH3

(VI)

H2 N
+ NH2
X
-

- I, II, - .
I III IV, II V VI,
(
,
, ).
( ) ,

1198

1199

, - , , ,
,
. (-I)-,
,

, I
IV. , ,
- (VI), - (V),
II VI. (+I)-, ..
, .
III V IV
VI.
, , ,
. (
)
, .. C N
,

(-M)-,
.

15.1,

.
15.1

XC6H4Br KNH2/NH3 (%)

-XC6H4Br ( I)

-XC6H4Br ( II)

<1

> 99

20 25

75 80

CN

10 15

85 90

05

95 100

OCH3

05

95 100

45 50

50 55

CH3

55

45

60

40

85 - 90

10 - 15

100

(-I)-,

- ( IV) I
- II. (-I)-
(. 2.3, .1), (-M)-

1199

1200

. NH2 X = CN VI
( II),
V, , VI V
- , - CN-.
, III IV ( I) CN
III; ,
, IV,
X. ,

(-)

, II (-) (. . 15.1).
, .
(+I). O- ( )
(+I)- (+M)- (. .2),
CN (-I, -M-).
15.1.4.

, .
,
. 1,2 (3,4- 3,4):

1200

1201
F
+ [(CH3)2CH]2NLi

[(CH3)2CH]2NH
; -780

N[CH(CH3)2]2
N[CH(CH3)2]2

[(CH3)2CH]2NH

; -780

(13%)

(87%)

COO

N N

t0

(60%)

Cl
Br
N

O
Li - Hg

Li - Hg

N
(9%)

15.2. SRN1

1970 . . -

. SRN1 (
-,

).

.
-

,

Nu:-. -.

- ArX-, -
- Ar. Nu-

1201

1202

- ArNu-. -
ArNu- ArX .
-
:
.-

ArX + e

ArX
Ar + X .
.
Ar +.Nu
ArNu
.ArNu + ArX
ArNu + ArX

.-

ArX

Ar . +

ArH

, Nu-
Ar, -
. -
.
(15.1)
SRN1-, -

. ,

SRN1

. SRN1
, Z , Nu- - :
-

ArZ + e

.
Ar
.-

Nu

.-

ArZ

ArNu

ArNu

ArZ

,

.
-,

-,

,
1202

-,

1203

, R3-, = Si, Ge, Sn,

, - - (. 15.2).
15.2

SRN1

F + C6H5S

SC6H5 (96%)

NH3 .

1.
Cl + C6H5S

SC6H5 (90%)

NH3 .

SC6H5

2.
-

I + (RO)2P-O K

H3C

NH3 .

O
P OR (95%)
OR

H3C

3.
Br + CH2 C
+ - O
K

CH3

C6H5CH2COCH3 + (C6H5)2CHCOCH3

NH3 .

(86%)

(14%)

4.
h

O K + C6H5Br

NH3 .

(72%)

C6 H5

5.
CH3
H3C

CH3

Br + CH2

CH3

NH3 .

H3C

CH2
CH3

N
(89%)

6.
C6H5

O
C

Br + K

CH2 -CN

h
NH3 .

C6H5

O
C

7.
CH2CN

Cl
+

+ K CH2 -CN

NH3 .

1203

(89%)

CH2CN
(97%)

1204

8.
9.
10.

C6H5Br +

NH3 .

HC
C6H5
O 5 6
C
6H5C CHH
CH
(65%)
2
3
NH3 .
CH3
H3C C C CH(23%)
(57%) O
2
N
H3C
CH3
h
(24%)
I + H3C CH C CH2CH3
NH3 .
- O
CH3
CH3
CH3
h
CH3 CH3 O CH3
+ H3C CH C CH2CH3
NH3 .
C C CH
- O
Cl
N
N
CH3 CH3
(98%)
N + CH2 C
CH3 - O

Br
H3C

CH3

11.
12.
CH3

O
O
Br + CH2 C C H C CH3

H3C

CH3
h
NH3 .

O
O
CH2 C CH2 C CH3

H3C

CH3

CH3

(82%)

13.
CH3

CH3
O
I
CH3

CH3

(CH3)3COK, h

CH3

(99%)

14.
C6H5Br + (CH3)3SnNa

h
NH3 .

C6H5Sn(CH3)3

(87%)

15.
CH3

CH3
I + KNH2

K
NH3 .

NH2

CH3

(64%)

CH3

16.

H3C

K
NH3 .

I + KP(C6H5)2

P(C6H5)2

H3C

17.
I + (C2H5O)2POK

h
NH3 .

1204

O
P OC2H5
OC2H5

(90%)

(88%)

1205

18.
19.
. 15.2
SC4H9
-

+ C4H9S Na
Cl

NH3 .

(72 - 85%)

.
, ,

,
SRN1, . , ,
-
95% - (. . 15.1),
.
-
:
.-.
KNH2
NH3 .

NH2
Br

- Br

KNH2

OCH3

OCH3

Br

OCH3

OCH3

NH3 .

OCH3

Br
OCH3
KNH2; K
NH3 .

.-

1) NH22) - e-

NH2
OCH3

SRN1 ,
.
15.8.

1205

1206

15.3. SRN1

-
.
-

-NO2C6H4CH2Z

SRN1-

(. ,

1965).

(. . 22, .3),
,
:
O

N + R CH2X
O

C CH2R
2
R NO2

C -

C N

O
3

OCH2R

O -

SN2-

(O-

), :
O

O
(CH3)2C N + -XC6H4CH2Cl
- O
(CH3)2C=N-OH + X

(CH3)2C N

OCH2C6H4-X -

CHO
O
(X=H, Cl, Br, CN, C , Alk, CF3)
R

- 2-

1206

1207

C- 92% 6%

O-.
.

C-, O-
. , 0,2 1,4-
C- 92
6%, O- 6 88%.
, O-
SN2- , C - ,
SRN1- :
.O2N

CH2Cl + (CH3)2CNO2

O2N

(CH3)2CNO2 +

CH2Cl

.O2N

CH2Cl

O2N

CH2 + (CH3)2CNO2

O2 N

CH3 .
CH2 C NO2 + O2N
CH3
O 2N

O2N

CH2 + Cl

O2N

CH3 .
CH2 C NO2
CH3

CH2Cl

.-

CH3
CH2 C NO2 + O2N
CH3

CH2Cl

- 2-(4-)-2-
-.
SRN1 SN2-
(. 15.3).
SN2- ,

1207

1208

SRN1-.
15.3

-NO2C6H4CH2X 2-
X
, %

C-

O-

93

C6Cl5COO

93

Cl

92

(CH3)3N

, %
C-

O-

TSO

40

32

Br

17

65

81

SRN1- - (RS-),
-, - (RSO2-), -, -.
.

.
(. . 9), SN2
E2.
- -NO2C6H4C(CH3)2Cl

SRN1-:

1208

1209

CH3 CH
3
NO2
H3C
CH3

CH3
CH(COOC2H5)2
H3C
-

CH(COOC2H5)2

(90%)
NO2
CH3
NO2
H3C

(CH3)2CNO2

CH3
H3C
Cl
-

NO2

CN

(94%)
NO2
1 2
NHR R
CH3
1 2
NR R
H3C

(90%)
NO2
CH3
CN
H3C

(85%)
NO2
CH3
SO2C6H5
H3C

NO2
-

C6H5SO2

(90%)
NO2

(95%)
NO2

-.
-
: 4-(1--1-)
PyC(CH3)2NO2, - , -, 1,1

(. ):
(CH3)2C COOC2H5 +
NO2

NO2
(CH3)2C C(CH3)2
COOC2H5

; h

(CH3)2C-NO2

CN

CN
NO2

+ (CH3)2C-NO2

NO2
Br

- ; h

CH3
NO2
CH3

(84%)

NO2

NO2
- ; h

(89%)
NO2

(CH3)2C(NO2)2 + C6H5SO2

; h
250C

C6H5SO2

CH3
NO2
CH3

1209

(81%)

(95%)

1210

(CH3)2C NO2 +
Cl

; h

(46%)

200C

C(CH3)3
NO2

(CH3)2C NO2 + C H-COOC2H5

CN
Br

; h

(CH3)2C
CH-COOC2H5
NO2 CN
(78%)

250C

, ,- , ,
HNO2
120.
15.4.
SNAr

.
, ,
: NO2, NO, RSO2, N2+,
CN, ,

( SNAr, . , 1958).
. 15.4

OH-, OR-, SR-, RNH2, R2NH, NH2NH2 .
15.4

1.
O 2N

Cl + CH3ONa

O 2N

-H 3OH; 60 oC

NO2

2.

O 2N

Cl + C6H5O K

H2O; 150 oC

1210

O 2N

Cl (73%)
NO2
O-C6H5 (80%)

1211

3.

Cl + NaOH

OH (70%)

O2N

H2O; 150 oC

NO2

NO2
NO2

4.
O2N

NO2

Cl + C6H5NH2

NH-C6H5 (90%)

O2N

; 10 oC

NO2

NO2
N

F + HN

5.

; 10 oC

NO2

NO2

6.

O 2N

Cl + CH-COOC2H5

7.

O2N

Cl + NH(CH3)2

O 2N

; 20 oC

CN

NO2

(93%)

H2O; 100-130 oC

CHCOOC2H5
CN
(97%)
NO2

O2N

N(CH3)2

NO2

8.

O 2N

Cl + CH3O Na

; 100 oC

O 2N

OCH3

O 2N

I + C6H5S Na

H 3OH; 60 oC

O 2N

SC6H5

Cl + Na2S2

S-S

2H5OH; 80 oC

NO2

11.

(58-66%)

NO2 O2N

O2N

SO2CF3

C6H5SNa; 20 oC
H 3OH

O2N

C6H5ONa; 60 oC

CH3O
O 2N

SC6H5
NO2

NO2

12.
O 2N

Cl + KI

H 3OH
;
100 oC

O 2N

Cl + NH2-NH2

(96%)

SO2CF3
NO2(70%) (85%)

NO2

NO2

13.

(89%)

NO2

NO2

10.

(78%)

Cl

Cl

9.

(75%)

NO2

H 3OH; 80 oC

O 2N

NH-NH2
NO2

NO2
1211

(83%)

1212

, -.

SNAr-

SEAr-

, SNAr- ,
. SNAr-
- ,
,
. - ,
1902 . (VIII) 2,4,6 -.
OC2H5 -:
2,4,6-
CH3O OC2H5
O 2N
NO2
O 2N
NO2
CH3O

C2H5O

O 2N

NO2

NO2

OCH3
NO2

NO2

(VIII)

15.4.1. -

, ,
IX,
,
,
. C(6) C(1) C(2) (109),
100.
, IX,
: C(2) C(3), C(5) C(6) C(4)

NO2

C(3) C(4), C(4) C(5) C(2) NO2:

1212

1213

NO2
H3C O 1,51 2

NO2

1,41
4

H3C O

1,35

1,39

NO2

1,45

(IX)

:
Z Nu
NO2

Z Nu O
N

Z Nu

NO2

NO2

NO2

NO2

Z Nu

Z Nu
NO2

Z Nu
NO2

NO2

- -
(NO2; SO2R; CN)
(Z = H, OR, OAr), -
(, ).
- 13C.
Z OSO2R, ,
.
-, ,
, -, .
-
, ,

1213

1214

, 1,1-- () , -.
-
- .

2,4,6-

- :
OCH3
O 2N

OCH3
NO2

OCH3

O 2N

NO2 -OCH
3

CH3O OCH3
O 2N
NO2

NO2

NO2

NO2

- :
3,
1,3-- ( . ) 1,
1,1-- .
,
.

1,1--

-
Z -.
1,1--
.

(. . 13),
SNAr-

1,1--

,
, , ,
,
SNAr:
Z

Z
+ Nu

Nu

Nu
k2

k1
k-1

()

1214

+ Z
X

()

1215

1,1--
. ,
,
-, C Z.


Z. 9, SN2-
I > Br > Cl >> F.
SNAr
: F >> Cl > Br ~ I.

C F, , C Z SNAr-,
, . , , ,
-
(. ).
,
-, -

, :

O 2N

k1

X + R2NH

k-1

O 2N

NO2
k2

NHR2
X
NO2
(X)

O 2N

NR2 + R2NH2X
NO2

15.4.2.

1215

1216

(k 1 >> k1 )

d [M]
= 0 (. . 3, .1)
dt

,
(),
ArZ + Nu

k1
k-1

k2

ArNu + Z

:
=

k k2
k 1 + k 2

[ ArZ ][ Nu ]
(15.2)

(.. ) :
k =

k k2
k 1 + k 2

. , k,
:
M ( k2 > k-1) ( k-1 > k2).

, M ,
.
,

, .
(X)
. , ,
N,N- ,
Z, ,
B. H+
(E2) (E1cB) (. .3),
k3[B]. (15.2)
(15.3):

1216

1217

k1 {k 2 + k 3 [ B]}
[ ArZ ][ R 2 NH ]
k 1 + k 2 + k 3[ [ B]

(15.3)
(k-1 << { k2 + k3[B]},
= k1 [ ArZ ][ R 2 NH ]

(15.4)
M,
k k

kk
= 1 2 + 1 3 [ B][ ArZ ][ R 2 NH ]
k 1
k 1

(15.5)
:
k = k + k[B]

(15.6)
, Z
( k-1 >> k2). . 2,4-
OH-.
OH- ,
NaOH . , OH-
,
- (.. k-1 > k2).
PhO- ( (15.5) (15.6))
.
(15.4), .
,
c = k[ArZ]{R2NH] + k[ArZ][R2NH]2

(15.7)

SNAr-

,
,
.
, ,
, (Z) F >> Cl > Br
> I. , , , (Nu)
1217

1218

( k-1),
(k2).
, :
Hal

Hal

NO2

I
NO2

NO2

+ Hal

+ KI
NO2

NO2

NO2

Hal

Cl

Br

17

2000

1,4-- 2,4,6 - ,
. -,
, ( k 106 /).
(k1 )
.
(d[M]/dt=0) .
15.4.3.

1,1--

1,3-,

1,3,5-,

, 1,3,5-
-, -, -, CCl3-, R3-
- -:
O 2N

NO2
+ CH3O

- 3

NO2

H OCH3
O 2N
NO2

NO2

1218

1219

F3CSO2

SO2CF3

- 3

+ CH3O
SO2CF3

NO2
+ CH2

SO2CF3

H CH2CCH3
NO2

C CH3
O

NO2

O 2N

H OCH3
SO2CF3

F3CSO2

NO2

NO2

O 2N

+ CH(COOC2H5)2

H CH(COOC2H5)2
NO2

NO2

NO2

H CN
O 2N

NO2
+ CN

(H 3)3CH

O 2N

NO2

NO2

NO2

H O
O 2N

O 2N

NO2

NO2

+ O
NO2

OH

NO2

H
+ O

O 2N

NO2

NO2

O 2N

NO2
+ CCl3COOH

H CCl3
NO2
+ CO2

O 2N

NO2

NO2
H
O 2N

NO2
+ KF
NO2

18--6

O 2N

NO2

1219
CH 3CN

NO2

1220

H H
O 2N

NO2

O 2N

NO2

(C 4H9)3SnH; N(CH 3)4F

NO2

NO2

H
O 2N

NO2
+ (CH3)3SnLi

Sn(CH3)3
NO2

O 2N
; -10 o

NO2

NO2

-

(RCOCH2)2Hg RCOCH2Sn(CH3)3.
- ,
- .
, K3Fe(CN)6,
.
,
:
H CCl3
O 2N
NO2

Br2

O 2N

CCl3

NO2

NO2

NO2

H CH2COCH3
O 2N
NO2
K3[Fe(CN)6]

O 2N

CH2COCH3
NO2

NO2

NO2
H CN
O 2N

NO2

Br2

O 2N

CN

NO2

NO2
1220

NO2

1221

H CH2COR
O 2N
NO2

CH2COR
NO2

O 2N

C7H7 BF4

NO2

NO2

1,3- -

,
, .
. -
-
:
O

NO2

O
C NH

+ CN

NH
H

X
N

X
O

NH2
C
O

X
N

N
O

-H2O

COOH

H2O
-N2

(X = Alk, Hal, SO3H)

-.

, (. ):
O
S
O
CH3

-C4H9Li

1221

SO2

SO2
CH2Li
O S OLi
CH

1222

(.. )
.

. ,

2--4,6- -
:

CH3

O 2S

SO2
CH2

CH3

CH2

CH3

CH3
CH3

CH3

SO2

CH3

-C4H9Li

CH3

SO2

CH3

CH3

CH3

HOOC
1. CO 2
2. H 2O

CH2

CH3
H

KOH; t
HOH

CH3
O
O
S
CH2

CH3

CH3
O
O
S
CH2

CH3

1,1--

1222

X Ar

X H

1223

, 1,2--.

,

, X = S, Y =
NR:
O 2N

H2C
SCH2CH2NHCH3
S
O 2N
NO2

O 2N

H3C N CH2CH2S
NO2
O 2N

NO2

NO2

NO2

NO2

CH2
N CH3
NO2

O 2N
S

N
CH3
15.4.4. SNAr

SNAr

N
NO2 CH3

,
X,
,
.

C6F5X, , -,
SNAr , , ,
.
, ,
SEAr - -,
SNAr -. , , SEAr -, SNAr --

1223

NO2
F

NO2

NO2
NH2

1224

. ,
95% 2--3,4,5,6- 4-2,3,5,6-:

NH2, -OCH3, -O-, CH3

-:
NH2

NH2

OCH3

+ CH3O
F

F
F

F
( )

, - ( SEAr --), -
, , :
H

OCH3

+ CH3O
F

OCH3

F
F

OCH3

F
+ CH3O
F

F
F

OCH3
+ CH3O
F

(15.5)
SNAr .

,
.

1224

NO2

NH2

1225

2,5--- .
2,
- ,
5:

, 2

, NH3 5.
, 2-NO2- ,
5 . 2,3 2:
CH3

CH3
NO2

NH3

NH2
NO2

NO2

, ,
,
-:
NO2
H3C

CH3
SNAr

CH3

H3C
Cl

15.4.5.

,
(SNAr, SRN1, ..),
.
, -,

1225

1226

-
. ,

-,

H Nu.
-. ,
,
KOH (H_ = 26; . 3),
, -
- (. ):

NO2

NO2

NO2

CH2SO2Ph
+

+ ClCHSO2Ph

CH2SO2Ph
, CH2SO2Ph,

CHClSO2Ph. ,

- .
- -, :
O

NO2

O
+

B
-HCl

+ ClCHSO2Ph
H

CHSO2Ph

NO2

CH2SO2Ph

CH2SO2Ph

Cl :
1,3,5-

NO2

NO2

ClCH2SO2Ph
KOH,

NO2

NO2

CH2SO2Ph
NO2

PhSO2CH2

CH2SO2Ph
NO2

, H-
H+, Cl-,

1226

1227

-, ,
( .
vicarious , ).

,
CH-,
(, KOH).
- X ( Cl), HX
-:
NO2

NO2
1. B

+ RCH-Y 2. H
X

NO2

R
CH Y

+
R CHY

Y ( ): SO2Ph, SO2C(CH3), SO2OPh,

SO2NR2, SOPh, P(OPh)2, P(OEt)2, CN, COOR ..
(): Cl, PhS, PhO, CH3O .;
R = H, Alk, Ar, PhS, Cl ( CHCl3)

15.4.6. SNAr

SNAr
. ,
(C6H6)Rh(C5Me4Et)(BF4)2 (XI)
80, 7%.
. -
(XI) , (XII). -
,
SNAr , .
:
+

Me

Rh2 Me

Me

Et
Me

+ F

CH3NO2; 80 o
-C6H6

1227

OMe
+

1228

- (XII)
,
2,4,6.
15.5.

SNAr, (.

),
. ,

,
,
. 13 ,
,
SNAr,
- .
-
- (.2). Z ,
(
Z), C6H5Z - . 13 , - ,

1228

1229

Z I II , .. -
-: Z - , - ,
() -C--C,
Z - , Z, -C C. - .
Z -, (
) Z, -C -C,
-C -C.
Z ,
-C -C -C -C.

, ,
Z - (.. (+M)),
- -, - -,

- - .
( (-M))
,
-, -, -, -.
? ,
, p-
, .

,
F

NH2

0,57

0,31

0,56

0,33

0,58

CN

NO2

0,66

0,38
0,35

0,33

0,31
0,14
0,05

0,14
0,44

0,33

,
- - - -

1229

1230

,
. Z = F NH2
- , , , - - .

-,

-.
-
- -. -
,
( ) - :
NH2

H2N

Z = NO2 CN (. ),
- -. -
, --
Z ( , , NO2
- -), NO2-, CN-

( ), ,

--,

.
, -- H-,
, .. .
1,3- , -,
C(3).
,
- . .

1230

1231

13 ,

.
. :
NO2

NO2

0,10

0,38
0,35

NO2

0,08

0,12

0,14

0,03

0,44

0,11
~0

0,02

0,16

NO2
0,10

0,15

0,10

0,31
0,33

~0
0,16

~0

, - - , , -
- .
--
.
15.6. ANRORC

ANRORC
.

,

-.

(. --, 1970). 2--4,

15

N, KNH2

15%
SNAr 2--4-,
. (85%)
- 6

1231

1232

, 2--4-,

15

C6H5

C6H5
*

Br N

NH2

N
NH2

N
NH2

N
C6H5

H2N H

C6H5

N
*

N
H2

*N

NH2

C6H5
*

N
C

Br

-Br

NH2

Br

H2N

(15%)
*

C6H5

C6H5
*

-Br
*

Br

C6H5

H2N

(85%)

ANRORC- (Addition of Nucleophile followed by Ring Opening
and

Ring

Closure).

,
.. (1976 1980).
:
R

R1
R2

H
A

HO

R2
HO

D
H

H
A

R2

-OH

R1

OH

R1

NR1

R1

R2

A
O

R1
A

D
H

1232
(A, B, D - N)

1233

,
2-,
,
,
:
OH

O 2N

CH3

O 2N
HO

CH3

O 2N
N

O 2N

CH3

OH

OH

CH3

CH3
CH3NH2

N
H3C

(85%)

CH3

H3C

N
CH2COOC2H5
CH3

O 2N

NHCH3
CH2COOC2H5

O 2N

OH

OH

N
CH2
CH3 I

N
CH3
CH3 I

O 2N

O 2N

H
HO

O
H

CH2
N
CH3

O 2N
(40%)

NHCH3
1233

(69%)

N
CH2
CH3

1234

N- 2- :
N
N

OH

R N
H

N
R

15.7.
SN1

-.

SN1

-. , C6H5+
(. ),
sp2-
, .. ( XIII):
sp2-

(XIII)

-
-. , sp2-
,
p- (. 9). ,
sp2-
, - sp2- (- ), -, ..
. , .
- (223

1234

1235

/).
-.
C6H5Cl C6H5+ + Cl- + H0; H0 = + 223 /
CH2=HCl CH2=CH+ + Cl- + H0; H0 = + 223 /
(190 /) -
(174 /)
.
.

, - ,
. ,

, .
, , ,
(XIII). , ,
, ,
. ,
:

(XIV)

, ,
p- sp2- ,
. , (XIII)
(XIV) , , , .
-
,
.

,
-,
:
Ar

N N

-N 2

Ar
1235

NuH

ArNu + H

1236

(Nu = H2O),
(. 23, .3).


. , v H2O D2O
. ( )
, .
SN1-,
, ,
SNAr.
ArN2+ D2O
.

- .
,

15

N,

:
[ArN

[Ar N

15N]

15N]

[Ar 15N

N]

, , , ,
- [Ar+NN]:
Ar
Ar 15N
Ar

15N

Nu

ArNu

15N

Ar + N2

,
[Ar+NN] Ar+, ,
H2O, OH-, F-, Cl-.
-

1236

1237

SN1

Ar, (
H+ -), SNAr-
, -+NN.

( 15, 19 87%
):
N N
CH3O

N N

+ NO2

CH3OD
SNAr

H(D)

CH3O

OCH3

CH3OD

OCH3

OCH3

NO2

CH3O
CH3OD

CH3O

NO2

CH3OD

NO2

15.8.

(I-, Br-, CN-, SCN-, N3-),
(I), - (. 22, .3),

Ar+ -
[Ar+NN].

( )

1237

1238

, .
SET- (Single Electron Transfer; . . 20).

-:
ArI + N2 (70-90%)

ArN N + I

, SRN1 , 15.2:
:
ArN2

+ I

ArN2

+ I

:
ArN2

Ar + N2

Ar + I

ArI

ArI + ArN2

ArI + ArN2

..

-
, - :
(45%), (15%), (10%)

(15%),

.
, ,
SCN-, (RO)2PO- .

,
.
ArN2+

X-

, : (1)
,

(2)

:
ArN + X
2

ArN2X

1/2(ArN 2)2 + 1/2X2

1238

1
3

(3)

1239

X- ArN2+
(ArN2)2.
,
, .
Ar-N=N-Ar (ArN2)2

ArN2+

X-

. , ,
Ar-N=N-X,
,
. Ar-N=N-X MX,

N N

N N X + MX

X
M

X + MX + N2

-,
(XV),
ArN3 :
Ar

N N + N3

Ar

N N
(XV)

Ar

N N N + N2

N N

,
C6H5N2+
:
(C6H5N2)2

2C6H5

1239

+ 2N2

1240

2C6H5

O
2C6H6 + HC-H

+ CH3OH

,
SN1 - ,
X- Ar-N=N-X

SET-,
,

1240

1241

16

16.1. ......................................................... 1243
16.2. ..................................................... 1247
16.2.1. ........................................................................................ 1247
16.2.1.. ................................................................ 1247
16.2.1.6. ............................................................................................ 1247
16.2.1.. ..................... 1248
16.2.1..
-1.............................................................................................................................. 1249
16.2.1.. () ................................ 1249
16.2.2. .................................................... 1250
16.2.2.. ............................. 1251
16.2.2.. 1252
16.2.2..
2- .......................................................................... 1253
16.2.2..
........................................................................................................ 1254
16.2.3. ................................................................................................ 1255
16.2.3.a. * '............................................................. 1255
16.2.3.. ........................................................... 1255
16.2.3.. - ..... 1256
16.2.3.. ...................... 1256

16.3. ............................................................ 1258

16.3.1.
...................................................................................................... 1258
16.3.1.a. .............................................. 1262
16.3.1.. 1265
16.3.1.. ............................................................................... 1269
16.3.1.. ................................................ 1272
16.3.1.. .............................................. 1275
16.3.1.. .

.................... 1276
16.3.1.. .
........................................................................................................ 1279
16.3.2. ...................................................................................................... 1285
16.3.3.
........................................................................................ 1292
16.3.4. ,-
.................................................................................................................................... 1294
1.3.4.. ................................................ 1295
16.3.4.. ................ 1296
16.3.4.. 1299
16.3.5. ,- ........ 1300
16.3.6. .................................................... 1304
16.3.7. ................................................................. 1311
16.3.7.. ( ) ........................................................................................................................... 1313
16.3.7.. ........................................................................ 1315
16.3.8. ............................................................................................. 1318
16.3.9. ................................................................. 1320

1241

1242

=O. ,
,
. ,
, .
O

R C

R C

-
.
C

=O 1,203

-=O 121,8

C-H 1,101

-- 116,5

. , 120,

sp2 .
- . -

pz- pz- .
,
.
, , - , , -
. ,
.

.

.
:
1 +

R C

+ H

R C

R2

1242

OH
R2

1243

,
, . , ,
82%- , ..
. a = -7,2
(3)2=+. ,
3+ -1,7, ..
. ,

.

16.1.

(. 16.1).
,, ..,
, .

CH3 CH CH2CH2C
Br

CH3 CH CH2 C
OH

,
:
O
CH3

C CH2CH2CH3

(CH3)3C

C CH2CH3

:
O
BrCH2CHC CH
3
CH3

1243

1244

,
(. . 16.1).
,
,
:
4
3 2 1 O
5
CH3CHCH2CHC H
Cl
OH
6

2--4-

CH3CHCHCH2CH2C
H
CH3 CH3

4,5-

,
:
C

CH3

O
H

CH3

2,3-a

:
O
CHO
2-

,
.
16.1

-93

-21

0,82

HCHO

-20

-123

1244

21

0,78

1245

-81

49

0,81

3(2)2

-99

76

0,82

2--

CH3-CH(CH3)-CHO

-66

61

0,79

3(3)3

-91

103

0,82

3(2)4

-57

131

0,83 ,

3(2)5

-45

155

0,85

C6H5CHO

-56

179

1,05

652

33

193

2=

-88

53

0,84

2-

3=

-77

104

0,86

2--

-64

197

1,16

n-364

205

1,02

-364

196

1,04

-364

199

1,02

82

285

--

--

--

3--4-

CH3O
HO

HO

33

-95

56

0,79

323

-86

80

0,80

3223

-78

102

0,81

-2

-3

3223

-42

102

0,81

-2

3(2)33

-57

127

0,83

124

0,82

-3
-2

3232

3(2)43

-36

151

0,82

32(2)3

-39

148

0,82

3737

-33

144

0,82

-3
-4

1245

1246

-48

-58

130

0,95

-510

-45

157

0,94

653

21

202

1,02

C6H5COCH2CH3

21

218

1,01

C6H5COC6H5

48

305

1,09

-3--2

-6

80

0,86

(3)2=3

-59

131

0,86

11

232

0,99

3=2

4--3--2

6537

,
, ,
, ,
.
:

CH3

CH2CH2CH3 O
CH3CH2 CH CH2C CH2CH3

Cl

2--4-

5--3

, , -
,
:
6

CH3C

CH2CHCH2CHO

3--5-

CH3

-
.

1246

1247

16.2.

.
.
.
.

16.2.1.

16.2.1..

.11,
:
1) H3(CH2)5CH2OH
1-

CrO3.2C5H5N
CH2Cl2; 25 oC

CrO3.C5H5N.HCl

2) CH3(CH2)4C CCH2OH CH Cl ; 25 oC
2 2

CH3(CH2)5CHO

(93%)

CH3(CH2)4C CCH2OH
2-
(84%)

-2--1-

3) HC CCH=CCH2OH
CH3

MnO2
CH2Cl2; 25 oC

HC CCH=CCHO
(72%)

CH3

16.2.1.6.

(.5). ,

. ,
, :

1247

1248

1) O3; CH2Cl2; -78 oC

2) Zn + CH3COOH

CH2CH3

1-

O
H3CH2C-CH2CH2CH2CH2CHO
6- (86%)

OsO4 NaIO4 (.5).
1) OsO -

CH3(CH2)9CH=CH2 2) NaIO4 - H O
4
2
1-

CH3(CH2)9CHO

(68%)

16.2.1..

, , ,
.
.18 (.3),
.
:
O
CH2C-H

O
CH2C-Cl H ; Pd/BaSO
2
4

1)

O
2) ClC

25 oC

O
CCl

3) H3(CH2)10COOCH3 +

(70%)

LiAlH[OC(CH3)3]

-78 oC

(CH3)2CHCH2

AlH

(CH3)2CHCH2

O
HC

(77%)

-78

(-)

4) (H3)3CCOOCH3

LiAlH2(OCH2CH2OCH3)2

25 oC

1248

O
CH

H3(CH2)10CHO
(88%)

(CH3)3CCHO

(81%)

1249

O
1) LiAlH(OC2H5)3;
5) (CH3)3CC-N(CH3)2
(CH3)3CCHO
2) H2O

(88%)

16.2.1..
-1

CH3(CH2)5C CH + (Sia)2BH
H2O2
NaOH

CH3(CH2)5
H

C C

H
B(Sia)2

CH3(CH2)6CHO (70%)

.7.
,

:
Cl

RC CH
H
CH3OH

1
R3 SiH

1
RCH=CHSiR3

RCH2CH(OCH3)2

H
H2O

COOOH

RCH CHSiR3
RCH2CHO

16.2.1.. ()

.


.
.

,
(.27, .3):
RCH=CH2 + CO + H2

Co2(CO)8
150 oC; 100-35-

RCH2CH2CHO + RCHCHO
CH3

1249

1250

,

Pt(II)
- (C5H5)2ZrHCl:
CH3CH=CH2 + CO + H2

(C5H5)2ZrHCl

CH3CH2CH2CHO

,
. ,
(II) (II) ( ).
:
CH2=CH2 + PdCl2 + H2O

CH3CHO + Pd + 2HCl
PdCl2 + Cu2Cl2

Pd + 2CuCl2
2Cu2Cl2 + O2 + 4HCl

4CuCl2 + 2H2O

,

.

:
C H3O H

600-650 o C; Ag

H C HO + H 2

16.2.2.

.
,
,
.

1250

1251

, - , - .
.

16.2.2..

.
,
.
. 50-60%.
1) O2N

CH3
H2SO4

CH3
H2SO4

H2O-CH3CH2OH

CHO

CrO3; (CH3CO)2O
H2SO4

OHC

3)

O2N

H2SO4

O2N

H2O-CH3CH2OH

2) CH3

CrO3; (CH3CO)2O

CH3

CH(OAc)2

(90%)

(AcO)2CH

CHO

CH(OAc)2

(50%)

1) CrO3; (CH3CO)2O
2) H2O

CHO
Br

Br

(45%)

,
. -
65%- -
.

(IV) :
ArCH3 + Ce(IV) + NO 3

ArCH2ONO 2 + Ce(III) + H

1251

1252

HOH

ArCH2ONO2

ArCH2OH

Ce(IV)

ArCHO + Ce(III)

50% 500 ,
.

65l:
C6H5CH2Cl

H2O; Fe

C6H5CHO + HCl

100 oC

16.2.2..

, N-- N ,
. (1913 .).
(),
,
:
N

N
ArCH2X + N

CHCl3

ArCH2

N
N
X

ArCH2-NH2 + HCHO + NH3

H2O

ArCH-NH2
H +
CH2=NH2

ArCH=NH + CH3NH2

H2O
+

ArCHO + NH3 + CH3NH2

- ArCH2NH2
,
. -
.
1252

1253

50-80%:
CHO

CH2Cl
1) (CH2)6N4; CHCl3
2) CH3COOH-H2O

(75-80%)

CH2Cl

1) (CH2)6N4
2) CH3COOH-H2O

CHO

(50%)

ArC2N+C5H5-,
. , , ,
:
ArCH2Br
(CH3) 2N

C5H5N

N=O

ArCH2NC5H5Br
O
Ar CH N
N

ArCHO + (CH3)2N

NaOH

ArCH-NC5H5

N(CH3)2

H2O
+

NHOH + HN

,
,
.
,
.11.

16.2.2..
2-

2- :

1253

1254

ArCH2Hal + H3C-C-CH3
N

CH3

C2H5OH

C CH3
N O CH Ar

ArCHO + (CH3)2C=NOH

, ,
,
. , 2-
- (.15).

16.2.2..

, .
,
.
. (1925),
,
SnCl4, .
,
.
:
ArC N + HCl

Ar

C NH
Cl

Ar

C NH + SnCl2 + HCl

[ArCH=NH2]2 SnCl62-

Cl
[ArCH=NH2]2 SnCl62-

ArCHO

1254

(60-90%)

1255

.
. :
O

Cl

ArC-NHC6H5 + PCl5

ArC=NC6H5 + POCl3 + HCl

Cl
[ArCH=NHC6H5]2SnCl62-

ArC=NC6H5 + SnCl2 + HCl

H2O
+
H

[ArCH=NHC6H5]2SnCl62-

ArCHO
(70-90%)

16.2.3.

16.2.3.a. * '
CrO3.2C5H5N

1) CH3CH(CH2)5CH3 CH Cl ; 25 oC
2 2
OH 2-
2) (CH3)3C

OH

CH3CO(CH2)5CH3
2- (97%)

CrO3-H2O-H2SO4
(CH3)3C
; 25 oC

4-- (90%)

4--

3) PhCH C CH

CrO3-H2O-H2SO4
; 25 oC

OH

PhC

C CH

(80%)

16.2.3..

1) H3(H2)3 CH + HOH
1-

2)

C CH
OH

+ HOH

H2SO4; HgSO4
CH3(CH2)3C-CH3
H2O
-2 (80%)

H2SO4; HgSO4
H2O

. . 11
1255

O
C CH3
OH

(67%)

1256

16.2.3.. -

1) B2H6;

1) H3CH2C CC2H5 2) H2O2-NaOH CH3CH2CCH2C2H5

O
3-

3- (60%)

16.2.3..

(., 1935):
1

RC

O
Cl

+ R 2Cd

R COR2 + R2CdCl
(30-60%)

,


(.., .., .., 1969).
, -20-(-78) ,
:
1

RC

O
Cl

+ R 2Hg

AlBr3
H2Cl2; -20 oC

R COR2

(75-100%)

-, - -
(.19, .3):
CH3(CH2)4COCl + (-C4H9)2CuLi

-78 oC

CH3(CH2)4CO(CH2)3CH3
5- (79%)

,
. ,
, ,
1256

1257

, , ,
, ,
-, ,
.
-, -, Th-
350-450 :
O
RC O
Ba

350-450 oC

RCOR + BaCO3

RC O
O
, ,
, .
,
,
.
, 80%

. 20%,
C9-C12 .
,
2-5%.
80% C5-C12
250-350 :
2 CH3(CH2)8COOH

Fe
300 oC

CH3(CH2)8CO(CH2)8CH3
10- (96%)

-
.13.

, :

1257

1258

CH3Li

CH2COOH

O Li
CH2C-O Li

CH2COOLi

HCl; HOH
0 oC

OH
CH2C-OH

CH3

-H2O

CH3Li
-; -10 oC

CH3

O
CH2-C-CH3 + H2O
(76%)

16.3.

:
1) ;
2) - ;
3) .

16.3.1.

+

C O
-

.

. . 16.2
.
16.2
(D)

2,27

2,72

2,88

3,02

= .

1258

1259

- . -
,

.

, sp2
sp3 :
R
R

C O + Nu

O
Nu

(,
, , , , ,
.) (CN-, SO3-; -, .).
.
LiAl4; NaBH4; LiBH4,
,
. .11.

.

.
, ,
-.


.

: ,
, , .

:

1259

1260

O
1) R C-R2 + NuH

OH
R C Nu
1
R
2

OH
2
R 1 C Nu
R

2) R1 C O + NuH
2
R
OH2
2
R C Nu
1
R

R C Nu + H2O
2
R

,
, ,
.
.

. , ,
.

. 16.3
.
16.3

H0f

H0f

/ 25 oC

/ 25 oC

HCHO

-26,0

-39,7

32

-45,5

33

-51/9

322

-48,8

323

-57,0

3222

-54,5

3223

-61,8

3223

-61,8

, . 16.3, , 7-8 /
, .

1260

1261

.

. --- p-
, ,
. -
p- -

- .
- ,
.
. (+I)-

.
,
. ,

.

,
. (.5, .1),
RCH=CHR , RCH=CH2
.
-c sp2-Csp3 -
sp3-Csp3. - sp2-Csp3 sp3-Csp3 ,
.

-
sp2-Csp3 , .
, -,
. , sp2-Csp3
(1,50 ) 0,04 sp3-Csp3 .

1261

1262

sp2-Csp3 :
125 o

O
1,204 A

sp3

1,50 A

CH3

C sp2

121 o

1,124 A
114 o

G0. , G0 = -RTlnK, G0
K , G0

(. 16.1).

16.3.1.a.

,

.
:
1

R C O
2
R

R 2 C OH
R
OH

25 = 2280, 3 - 37
0,2 ;
25 10-3. ,

99,999% 2()2;
58%,
.
.

1262

1263

. 16.1.
NuH

- ,
,
. , ,
() 3104,
:
CF 3 CO CF 3 + H 2 O

( CF 3 )2 C(O H)2 ; K 25 oC = 1 . 10 6

,

.

, ,
.

, .
, ,
,
. , ,
, .
:

1263

1264

O
R C
H

+ HB

RC O...HB + HOH

O...HB
RCH

H
R C HO + B
O

H
H
H
R C HO + B

H
R C OH + HB
OH

O
H

,
:
H
OH
RCH
OH

O H

H
R
H

O H + HB

H ...O
H... B

C O... H O... H
H

H
,
. ,

.
, ,

- -:
O
B + H2O + RCHO

R C H + HB
OH
OH
R C H + B

O
R C H + HB

OH

OH

1264

1265

16.3.1..

, ,
,
.
:
1

OR2
R1 C OH

C O + R 2OH

:
2

OR
1
R C OH + R 2OH

OR2
1
R C OR2 + H2O
H

.
,
- ,
:
OR2
R1 C OH + H
H

OR2
1
R C OH2

R C OR2 + H2O

H
2

R C OR2 + R2OH
H

OR H
1
R C O
R2
H

R OH

OR2
1
2
2
R C OR + R OH2
H

, 1, -

1265

1266

,
:

O2N

O
C + 2CH3OH
H

CH3CHO + 2CH3CH2OH

HCl

O2N

CH

OCH3
OCH3

(75-85%)

CH3 CH
(60-64%)

OCH3
OCH3

,
,
.

.
- ,
H :

HCHO + 2CH3OH

H2C(OCH3)2 + H2O

CH3CHO + 2CH3OH

(-19,0 /)

CH3CH(OCH3)2 + H2O

CH3COCH3 + 2CH3OH

(CH3)2C(OCH3)2 + H2O

(-15,2 /)
(-11,7 /)

,
. ,
. ,
,
G, G
,

G = TS

,
.
. , ,

1266

1267

.
, 1,2- 2,3. ,
, 1,3- 2,2--1,3 :
O
+ HOCH2CH2OH

H3PO4

+ H2O

110 C; 4
(80-85%)

CH3
O

CH3
CH3
CH3C6H4SO3H O
+ HOCH2-C-CH2OH

CH3
O

(83%)

CH3

C6H5CHO + CH2CH2OH
OH

CH3 + H2O

110 C

O CH2
C6H5CH
+ H2O
O CH2
(73%)

1,3-
1,3-. -

-:
R
R

C O + HC(OCH2CH3)3

CH3C6H4SO3H

R
C
R

OC2H5

O
+ HC

OC2H5

OC2H5

.
, ():
n CH2O

HO-(-CH2-O-)n-H

180-200
. ,
37%- .

1267

1268

- ;
.
.
CH3
O

O
O

CH3

O
CH3

.

.
.

- - ,
, .
, ,
,
:
O
CH3C6H4SO3H
O
1) BrCH2CH2CH2C-H + HOCH2CH2CH2OH
BrCH2CH2CH2
CH3(CH2)3

CLi

O
CH3(CH2)3C CCH2CH2CH2

CH3(CH2)3C C(CH2)3CHO
2) CH3C(CH2)3COOCH2CH3
O
1) LiAlH4;
2) H2O

HOCH2CH2OH
H

CH3-C-(CH2)3CH2OH
O
O
CH2 CH2

H3O

H2O

(90%)

CH3-C-(CH2)3COOC2H5
O
O
CH2 CH2

H3O
H2O

CH3C(CH2)3CH2OH
O

1268

1269

OCH3 ~700 oC

OCH3 + CH3OH

OCH3

16.3.1..

()
.
, :
CH3

CH3
HSCH2CH2SH; BF3.O(C2H5)3

0-20 C

S
CH2

S
CH2

CH2CCH3
O

(99%)

H2 C CH3
S
S
CH2 CH2

HSCH2CH2SH; ZnCl2
(C2H5)2; 25 oC

(95%)

,
.
2-. :

20-50 ,
:
R1
2

C O + HSCH2CH2SH
Ni + H2
CH3CH2OH

BF3.(C2H5)2O
CH2Cl2

R CH2R

1269

R1
2

CH2

CH2

1270

CH3
Ni + H2
20-40 oC

S
CH2

CH3

H
H

CH2

(60%)

1,3- 1,3-.
H
C
H

OCCH3
OCCH3

+ HSCH2CH2CH2SH

BF3.Et2O
CHCl3

S CH2
H2C
CH2
S CH2
1,3- (80-85%

1,3- -
(= 31). ,
, . 1,3-
.
1,3-
(, , 1969-1970 .):
S CH2
S CH2
-C4H9Li
R1X
LiHC
CH
H2C
CH2
2
-
-
S CH2
S CH2
R1

S CH2
HgCl2
C
CH2
R1CHO + HSCH2CH2CH2SH
CH3OH-H2O
H S CH2

:
S CH2
S CH2
2
C
H
Li
RX
4
9
1
1
LiR C
CH2
R HC
CH2
-
-
S CH2
S CH2
R1

S CH2
HgCl2
2
C
CH2
R1COR + HSCH2CH2CH2SH
2
CH3OH-H2O
R S CH2
, ,
,
1270

1271

.
1,3-
.
-
:
S CH2
H S CH2
1)-C4H9Li
1)-C4H9Li
CH2
CH2
C
CH2
2) CH3(CH2)4Br
2) CH3(CH2)4Br
CH3(CH2)4
S CH2
S CH2
(92%)

CH3(CH2)4
CH3(CH2)4

S CH2
CH2
C
S CH2

S CH2
1)-C4H9Li
CH2
CH2
2) Cl(CH2)3Br
S CH2
S CH2
C
CH2
S CH2

HgCl2

CH3(CH2)4C(CH2)4CH3

CH3OH-H2O

H
Cl(CH2)3

O (87%)

S CH2
C
CH2
S CH2

HgCl2
HO-CH2-CH2OH-H2O

1)-C4H9Li

O (50%)

1,3-
. , ,
-:
CH3 S
H S

1)-C4H9Li
2) C6H5CHO

CH3 S
C6H5CH S

HgCl2
CH3CN-H2O

CH3COCHC6H5
OH (90%)

OH

1,3- :

1271

1272

-C4H9

S CH2
-C4H9
S CH2
1)-C4H9Li
C
CH2
CH
CH2
2) CH3-CH2-CH-CH2 CH CH CHCH
3
2
2
S CH2
S CH2
O
OH

HgCl2
CH3CN-H2O

C4H9COCH2CHCH2CH3
OH

1,3-
. ,
- 1,3. HgCl2 :
C6H5CHO + HS(CH2)3SH

S CH2
C6H5CH
CH2
S CH2

S CH2
HCl, HgCl2
C6H5C
CH2
CH3OH-H2O
S CH2
H3CH2

1) -C4H9Li;
2) CH3CH2Br

(50-75%)

C6H5CCH2CH3 + HS(CH2)3SH
O (74%)

16.3.1..

:
RC

O
H + HC N

OH

H
C
R

C N
OH

CH3CH2CH2

CH3CH2CH2CHO + HCN

C CN
H

CH3

CH3COCH3 + HCN

CH3

1272

(75%)

OH
C
C N

(78%)

1273

OH

O + HCN

CN

(60%)

1904 .
,
. , ,
,
. ()
pK 9,2.
-
, :
1) HCN + B

2) R C H + C N

HB + CN

O
O
3) H C CN + HB
R

H C C N
R O

H C CN + B
R OH

, - , ,
. HCN


(.. = 26 ).

-,
.

:

1273

1274

CH3CH2

O
C CH2CH3

(CH3)3SiCN
KCN; HOH

CN
CH3CH2

C CH2CH3
OSi(CH3)3

CN
HF
KF

CH3CH2

C CH2CH3 + (CH3)3SiF
OH

(90%)

.
.

, , - -:
HCN

CH3COCH3

(CH3)2 C CN

H2SO4
CH3OH

CH2

CH3

OH

C6H5CHO

(CH3)3SiCN

C6H5

C COOCH3
(90%)

OSi(CH3)3 HCl; 100 o

C6H5CHCOOH
C CN
H2O
H
OH (67%)

,
:
CH3
CH3

OH

OH

C
CN

CH3COCH3 + H2O + CN

:
OH
CH3CH2

C CN
H

1) LiAlH4
+

OH
CH3CH2CHCH2NH2

2) H3O ;

(80%)

,
.
.

1274

1275

16.3.1..

- :
O

H2O

+ NaHSO 3

RC
H

OH
RC SO 3Na
H

.
- -
.
, , ,

40%- :
O
CH3C

H2O

+ NaHSO 3

OH
CH3

C SO 3Na
H

H2O

CH3COCH3 + NaHSO3

(89%)

(CH3)2C-SO3Na
OH (56%)

,
.

- .
,
.
-
:

Cl

CHO
KCN
H2O

Cl

NaHSO3
HOH; 10 o

OH
C SO3Na
H

Cl

OH
C CN
H

1275

(74%)

1276

16.3.1.. .

-
.11.

,
(.
16.4).
16.4

C4H9MgBr

1) HCHO; ; 20 oC, 5
CH3(CH2)3CH2OH
2) H3O+, H2O; 0 oC
(92%)

MgCl

(CH3)3C-MgCl

1) HCHO; ; 20 oC

(64-69%)

1) HCOOCH2CH3; ; 20 oC, 24
(CH3)3CCH2OH
2) H3O+, H2O; 0 oC
(72%)

(CH3)CHMgBr

1) CH3CHO; ; 20 oC, 24
CH3
+
2) H3O , H2O; 0 oC

C2H5MgBr

C6H5C CH ; 20 oC
C6H5C

CH2OH

2) H3O , H2O; 0 oC

C6H5C CMgBr

CH3
CHCH OH
CH3 (54%)

1) CH3CH2CH2CHO; ; 20 oC
+
2) H3O , H2O; 0 oC

C CH CH2CH2CH3
OH

CH3CH2CH2CH2MgBr

(52%)

1) CH3COCH3; ; 20 oC, 24
CH3CH2CH2CH2
+
2) H3O , H2O; 0 oC
(90%)

1) C6H5COC6H5; ; 20 oC

C6H6MgBr 2) H O+, H O; 0 oC
3
2

1276

(C6H5)3COH

OH
C CH3
CH3

(89-93%)

1277

-
(.19),
:
O
(CH3)2CHMgBr + (CH3)2CHC-CH(CH3)2

; 20 oC

H
(CH3)2C=C-CH(CH3)2 + (CH3)2CH-C-CH(CH3)2
OMgBr

(65%)

(29%)

OMgBr

O
(CH3)2CHCH2MgBr + (CH3)2CHC-CH(CH3)2

; 20 oC

CH2CH(CH3)2
(CH3)2CH-C-CH(CH3)2 + (CH3)2C=C-CH(CH3)2 +
(8%)

OMgBr

(11%)

OMgBr

H
+ (CH3)2CH-C-CH(CH3)2
OMgBr

(78%)

, ,
,
.
,
:
O
(CH3)3CLi + (CH3)3C-C-C(CH3)3
OLi
(CH3)3C O C(CH3)3

; -78 oC

H2O; 0 oC

OLi
(CH3)3C O C(CH3)3
C(CH3)3

C(CH3)3

(81%)

. ,
, ,

1277

1278

. , ,
, .
,
, ..
.
,
, ,
-3:
CH3(CH2)5CHO + CH3MgBr

C2H5

CH3(CH2)5CHCH2CH3 + CH3(CH2)5CH
OH

OH

(R)--3 (50%)

(S)--3 (50%)

,
( ),
.
, ,
. , , 2
:
O
H
CH3

CH3
1) CH3Li
+

2) H3O

OH
H
CH3

90%
(1R, 2S)-1,2-

HO
+

CH3
H
CH3

10%
(1S, 2S)-1,2-

(1R; 2S)-
,
. (1S; 2S)-
, ,
2. ,

, (1S; 2S)- .
. 16.2
3Li .

1278

1279

(R)- (S)- , ,
, . ,
- (1R; 1S)
(1S; 2S) - . -

,
.

(.8).

. 16.2.

16.3.1.. .

1279

1280

.
( ), ( - ).
, ,
, :
NR
C

O
RNH2

R2NH

NR2

( )

,
.
-
.

,
-
(). .
,

- :
1

R1 C O + R3NH2
R2

R1 C OH
R2 NH

C O
2
R
NH2

R3

R3
1

R C OH2
R2 NHR3

-H2O

()
3

R C NHR
R2

C NR + H

:
1) CH3CHO + H2N(CH2)3CH3

CH3COOH
C6H6

1280

CH3CH=N(CH2)3CH3 + H2O
(83%)

1281

CH3COOH
C6H6

2) CH3COCH3 + H2N

+ H2O

CH3C=N
CH3

(95%)

1,2-
. N,N--1,2-
- ,
:
C6H5
CH2 NH

C6H5
+

CH2 NH

O
H

C R

CH2 N

CH3OH; H

CH2 N

C6H5

CHR + H2O

C6H5

.
,
.

- :
H
C C

R N H
R

C C

OH
C C

R
H H
R
-H2O

-H

C C
N

OH2
C C

C C NR + H

,
. -
- , :
1)

O + HN

-CH3C6H4SO3H
110 oC; ; 1

N
(75%)

1281

O + H2O

1282

H
N

2) CH3CH2COCH2CH3 +

3) 2 R2NH

-CH3C6H4SO3H
CH3C C
110 oC; ; 1
(90%)

(CH3)3SiCl

O
1

CH2CH3

+ H2O

R2N-Si(CH3)3 + R2NH2Cl

R2N-Si(CH3)3 + R CH2C-R

CH2Cl2

R1CH=CR + (CH3)3Si-O-Si(CH3)3
NR2

.
, ,
(3)3SiNR2 .
o
.
( > 9) ( < 1) ,
~3-5, .. .
,
.
.
. ,
, ,
(NH2OH; NH2-NH2 .)
, ,
. 3 5

,
, . . 16.3

:
CH3COCH3 + NH2OH

25 oC
H2O

CH3C=N-OH + H2O
CH3

1282

1283

,
, , , 2,4, n-,
, .
,
.
:
N OH

O + NH2OH

O
H

Cl

+ NH2CONHNH2
O
C + NH2-NH2
H

C6H5COCH3 + O2N

NH-NH2

CH N NHCONH2

Cl

CH N NH2

O2N

NO2

NH-N=CC6H5
NO2

. 16.3.

=O .
1911 . ..

1283

CH3

1284

. . ,
, . ,
(.. = 245 ) (.. = 287 ):

CHO

1) NH2-NH2 . H2O
2) KOH; HOCH2CH2OCH2CH2OH; 200 o

(60%)

CH3

.
O 1) NH2-NH2 H2O

2) KOH; HOCH2 CH2 OCH2 CH2 OH; 240 o

[3.3.0]
(90%)

[3.3.0]-2

O
CH3
O

CH3

1) NH2-NH2 . H2O
2) KOH; HOCH2CH2OCH2CH2OH;
210 -230 o

(69%)

- ,
.
- - (. .17,
.3) ,
.
-

:
1

R C

OH
H2O

N NH2 OH
H2O

R2

N NH
1

R C
2
R
H

R C

N N H H2O
2

OH

R
H2O

-N2

N NH
1

R C
2
R
H

H
1

R C H + OH + N2
R2

1284

1285

16.3.2.

, . 1954 .,

.

.
, .

, :
1

C O + (C6H5)3P

C R
H

()

R3

C C

+ (C6H5)3P=O

(65)3+-2-. ,
:
RCH2Br + (C6H5)3P

(C6H5)3PCH2RBr
(70-100%)

-
(65)3
, .
-
: , () (3Si)2N, - .
:
(C6H5)3PCH2RX

-C4H9Li
; -78 oC

(C6H5)3P-CHR + LiX + C4H10

,
,
(65)3=R. d .
, ,

1285

1286

, d-
.
-, - :
NaH

O + (C6H5)3PCH3Br
CHO
+ 2(C6H5)3PCH3Br
CHO

HC

CH2 + (C6H5)3P=O
(86%)

NaNH2

(75%)

C CHO + C12H25P(C6H5)3Br
HC

CH=CH2
+ 2(C6H5)3P=O
CH=CH2
Na N[Si(CH3)3]2
; -30 oC

C CH CH C11H23 + (C6H5)3P=O
(81%)

C6H5Li

O + (C6H5)3P
Br

+ (C6H5)3P=O
(45%)

D, , ,
, .
- ,
- 10, 12Z-1-. 12-10- -20 o ,
- () ,Z-
,
45%:
CH3OOC(CH2)8CH=CHCHO

CHCH2CH2CH2PPh3Br
Na N[Si(CH3)2] ; ; -20 oC

CH3CH2CH2CH=CH-CH=CH(CH2)8COOCH3 1) LiAlH4;
Z-

E-

CH3CH2CH2CH=CH-CH=CH(CH2)8CH2OH
EZ10E-12Z--1- ()

1286

2) H3O

1287

.
BASF () A1,
:
CH3

CH3

CH3

CH3ONa
CH3OH

P(C6H5)3X
CH3

CH3

CH3

CH3

CH3
C

CHCH2COOCH3

P(C6H5)3X
CH3
CH3

CH3

CH3

CH3
O

O
C CH3

HO
H2O

CH3
CH3

CH3

CH3

CH3
OH
1

CH3

.
, ,

,
.
.
. -20
-
:

1287

1288

O
2

R C C HR1
3
R

(C6H5)3P-CHR1 + R COR
O

P(C6H5)3

P(C6H5)3

(C6H5)3P= + R C C H
3
R1
R

R C CH
3
R1
R

, ,
.
-,

.
- -, - -:
(C6H5)3 P

(C6H5)3 P

(C6H5)3P-CHR1 + R CHO
H

R2

H
R1

(6H5)3P=O +

R2
R1

R2

R1

R2

-(Z)-

-()-

(C6H5)3P= , -
- ,

. '
(. . 7, .1),
.
, ,
(65)3=,
- -
- -.
. ,
1288

1289

- -,
, -,
, , . -/- , ,
, -. ,

-.
,
, , .
(C6H5)3P-CH-COOC2H5 + C2H5CHO

C6H6

C2H5

6 ; 80 oC

(49%)

COOC2H5

, .

- , ()-
. -.,
95-97%:
1

(C6H5)3P-CH2R + R CHO

[(CH3)3Si]2NNa
; -10-(-30 oC)

R1

R2

+ (6H5)3P=O

(Z)-

, -.

-25-(-80) .
, -,
, (65)3=.
:

1289

1290

PPh3

Li O
H

H
R

R1

Li
BuLi
-50 oC

PPh3

(H3)3COH

R1

H
R

R1
R

PPh3

-
-,
-.
-/- 95 : 5 97 :

3.
,
Z-
() , .


, (I) Z R1 R2:
2

(C6H5)3P-CHR1 + R CHO

H
O
P(C6H5)3
H

R2
R1
H C C H
O P(C6H5)3

R
H

R
H
P(C6H5)3

II

R2
H
C
C
H
R1
O P(C6H5)3
-

R2

R1

R2

R1

-()-

-(Z)-

I II,
-

1290

1291

. - II
-. R1 - ,
- (65)3 , -.
R1
, -
-,
- ( ).

. ,
,
- - - .

, .
.
:
O
1
R CH2P(OCH2CH3)2 + CH3CH2X

1) R1CH2X + P(OCH2CH3)3

O
2) R CH2P(OCH2CH3)2
1

O
R CHP(OCH2CH3)2 + BH

O
3) R CHP(OCH2CH3)2 + R2CHO
1

R1
H

R CH-C-H
R2
(CH3CH2O)2P=O

H
R2

O
+ (CH3CH2O)2P

, R1 ,
,
. -:

1291

1292

H
O
(C2H5O)2P-CH2COOC2H5

1) NaH;

COOC2H5
O
+ (C2H5)2P-O

O
2)

(70%)

- ,
:

; -
- -:
O
H2=CH-CHO + (C2H5O)2P-CH2COOC2H5
CH2=CH
H

C2H5ONa

H
(66%)

COOC2H5

+ (C2H5O)2P

(2H5O)2P()CH2COOC2H5 pKa = 15. ,
, 25- .,
:
O
(C2H5O)2P-CH2CN

1) NaH; C6H6
2) CH3O

CHO

CH3O
(88%)

H
C C
CN
H

16.3.3.

,
().
,
- :
1) (CH3)3S I + -C4H9Li

; -20

1292

(CH3)3S-CH2 + C4H10

1293

O
2) (CH3)2S

O + NaH

Na CH2SCH3 + H2

; 40-50

O
3) (CH3)3S Br + Na CH2SCH3

(CH3)2S-CH2 + NaBr + CH3SCH3

-; -10

, ,

.


.
, , SN2-pe
:
R1
R2 C CH2 S(CH3)2
O

R COR + (CH3)2SCH2
R1
2

C CH2 + (CH3)2S
O
(75-95%)

,
- :
O
1) C6H6CHO + CH2-S(CH3)2

CH3 C CH2 + (CH3)2S

H
(75%)

O
2)

3)

CH2 O
+ CH2-S(CH3)2

O + CH2-S(CH3)2

+ (CH3)2S
(97%)

CH2
+ (CH3)2S
O

; 0-20

(82%)

1293

1294

. -2+S(O)(3)2
:
(CH3)2S

O
(CH3)2-S-CH3 I

O + CH3I

(CH3)2-S-CH3 I + NaH

(CH3)2 S-CH2 + NaI + H2

O
+ (CH3)2S
CH2

(CH3)2 S-CH2 +

(75%)

16.3.4. ,-

,-

, 1,4- . 1,4 ,-
:
4

C
3

, 1,4-
. 1,2- 1,4 ,
,
. 1,2- 1,4- , :
O
C

+ H+Y

1,2-

1294

OH
C
C
C

1295

O
C

1,4-

+ Y

C
Y

- ,
-
. , ,
-
.
,-

,
.
1.3.4..

,
-.
:
H3

20 oC

C CH=CH2 + HN(CH2CH3)2

C2H5OH

O
O + CH3NH2

CH3CCH2CH2N(CH2CH3)2
O

(92%)

O
C2H5OH-H2O

CH3NH

(CH3)2C CH C CH3 + CH3NH2

O

H2O

(90%)

(CH3)2C CH2 C CH3

NHCH3

(75%)

,
,
.

1295

1296

16.3.4..

1,2- 1,4-- , .
,-
. ,-
R=CH(OH)CN 1,4-.
, - ,
:
35 oC
CH3COOH

C6H5-CH=CH-C-C6H5 + HCN
O

C6H5-CH-CH2-C-C6H5
CN

(93-96%)

,-
1,4- 1,2- .
1,2-,
1,4- - .
:
(CH3CH2)3Al + HCN

;
0 oC

(CH3CH2)2AlCN + C2H6
(93%)

-:

CH3

C
O

1) (CH CH ) AlCN;
CH=CH2 ;3 -202 o2 C
+
2) H3O ; H2O

CH3
CH3

C CH2 C CH3
O

CN
(88%)

-
,-:
H

1) (CH3CH2)2AlCN;
; -20 oC
+
O
2) H3O ; H2O

H
+

CN
-9--2

O
24:1

CN
-9--2

- 72%

1296

1297

16.3.4..

,-
(1,2-):
1)

OH

1) CH3Li;

(95%)

2) H3O ; H2O

CH3

OH
1) CH3Li;

2) (CH3)2C=CH C CH3

2) H3O ; H2O

(CH3)2C=CH C CH3
CH3

(81%)

.

- (; , 1966).
- ,-
, , .
, .
:
O
1) CH3C CH=CH2

2)

- +

1) [(CH3)2Cu] Li ;
+

2) H3O

CH3C CH2CH2CH3
(97%)

- +

1) [(CH3)2Cu] Li ;

2) H3O

(97%)

CH3

3)

- +

1) [(CH2=CH)2Cu] Li ;

2) H3O

(65%)

CH=CH2
3)

- +

1) [(C6H5)2Cu] Li ;

2) H3O

(70%)

C6H5

1297

1298

H
- +

1) [(CH3)2Cu] Li ;

4)

2) H3O

(80%)

CH3

9----2

,
-
(I) , .
(5-10%) Cu2Br2.
.
,
R2CuLi - ,-,
.
, u (I)
u (II). , -,
RLi RMgX.
, 1,4- ,
- , .
,
, (1,2). , ,
, 1,2- 1,4-.

. ,-
,
,

-
:

1298

1299

1) CH3MgBr

CH3CH=CH CH3

2) H3O

CH3
CH3CH=CH C CH3 +
(72%)

OH

+ CH3 CH CH2 C CH3

CH3

C6H5CH=CH CH2CH3
O

(28%)

1) CH3CH2MgBr
+

2) H3O

CH2CH3
C6H5CH=CH C CH2CH3 +
(30%)

OH

+ CH3CH2 CH CH2 C CH3

CH2CH3 O
C6H5CH=CH C(CH3)3
O

(70%)

1) CH3CH2MgBr
+

2) H3O

C6H5 CH CH2 C C(CH3)3

CH2CH3 O

(100%)

C6H5CH=CH C6H5
O

1) CH3CH2MgBr
+

2) H3O

C2H5
C6H5CH=CH C C6H5 +
(1%)

OH

+ C6H5 CH CH2 C C6H5

CH2CH3 O

(99%)

, . -
. 1,2- , ,
.
16.3.4..

,-
1,4-
,
- :

1299

1300

O
R3B + CH2=CH C

25 oC

RCH2 CH C

O
R3B + CH2=CH C

RCH2CH2C

RCH2 CH C

H2O

OBR2
O

OH
RCH2 CH C

R1

25 oC

OBR2
O

OH
RCH2 CH C

H2O

RCH2CH2C

R1

,
-
, :
CH3(CH2)3CH=CH2
O
CH2=CH C

B2H6

[(CH3CH2)3CH2CH2-]- 3B

25 oC

1) (-C6H13)3B; ; 25 oC
2) H2O; 25 oC

B2H6
; 25 oC

3B

O
CH3(CH2)7C
(83%)

O
CH
=CH
C CH3; ; 25 oC
1)
2
2) H2O

CH2CH2CCH3 (100%)
O
, ,
.
16.3.5. ,-

,-
1,2- 1,4-

1300

1301

.

. ,
,- ,
, ..
-10
- (-20) :
CH3CH=CH-CHO

1) LiAlH4; ; -10 oC
+
2) H3O ; 0 oC

CH3CH=CH-CH2OH
(82%)

1) LiAlH4; ; -10 oC
+
2) H3O ; 0 oC

OH
(97%)

,- ,
(-)
:
(-C4H9)2AlH
, -20

(95%)

OH

,-
:
O

1) Li; NH3 .; -33 oC

2) NH4Cl; HOH

O
H

CH3

H H

(50%)

CH3

- (.6, .1)

:
1)

C C C O + Li

+e

C C C O
-

1301

Li

1302

C C C O

2)

+ NH3

+e

C C C O
H

3)

C O

+e

+ Li

4)

C O

H2O

Li

C O

Li

C OH

LiOH

C O

H H

+ NH2

-,
-.
.
, ,
- , .
.

- :
CH3

CH3
O

C
CH3

1) Li; ; 20 oC
2) CHC3CH2OH; H2O

CH3
CH CH3
H

CH3

O (75%)
2--5-

:
CH3

CH3
1) Li; NH3 .; 20 oC

C
CH3

CH2 2) NH4Cl; H2O

CH3

CH2

C
H
CH3 (98%) CH3

,-


1302

1303

, -
.
-
, :
CH3

CH3
O

1) Li; NH3 .; 20 oC
2) NH4Cl; H2O

(90%) 10---2-

,
, , .
-, ,-
,

. .17, .3,
- 2, 2-2-.
O Li

O
CH3

CH3 Li; NH .
3

CH3
CH3

CH3I
(46%)

, ,-

-
.
- ,-

,
(3):

1303

1304

Pd/C
CH3COOCH2CH3

COOC2H5

O
(95%)

COOC2H5
Pd/C
CH3COOCH2CH3

O
(83%)

- ,
, .
,
= >=O; -(O)-OR -CN-py.

.
16.3.6.

.

: (.11)


(, , , ,
), .

- -
, :
CH2=CHCH2CH2CHO

NaBH4
CH3CH2OH

CH2=CHCH2CH2CH2OH

1304

1305

, , .
:
4, CH CH CH CH OH
1) CH3CH2CH2CHO 1) NaBH
+
3
2
2
2

2) H3O

2)

1) NaBH4,
+
2) H3O

4,
3) CH3(CH2)5CHO 1) LiAlH
+
2) H3O

(85%)

OH
CH
(88%)

CH3(CH2)5CH2OH
(86%)

O
1) LiAlH4,
+
2) H3O

4)

OH
(90%)

,

. ,
,
15. LiAlH4-AlCl3 :


. , 4- ,
LiAlH4 lCl3, - 4-,

80% - 20% - :
O
(CH3)3C

1) LiAlH4, AlCl3;
2) (CH3)3C-OH

(CH3)3C

OH
(99%)

LiAlH4
lCl3 :
BrC6H4COC6H5

LiAlH4, AlCl3;
; 36 oC

15

BrC6H4CH2C6H5
(90%)

HAlCl2, H2AlCl .,
.
1305

1306

:
O CH2

1) LiAlH4, AlCl3; ; 36 oC

OCH2CH2OH

2) H3O

O CH2

C6H5CH(OCH3)2

(94%)

1) LiAlH4, AlCl3; ; 36 oC
2) H3O+

C6H5CH2OCH3
(88%)

LiAlH4 1:1
,
, :
1) LiAlH4, AlCl3;

n-NO 2-C6H4-CHO

2) H3O

O
Br-CH2CH2C-Cl

n-NO 2-C6H4-CHOH
(75%)

1) LiAlH4, AlCl3;

BrCH2CH2CH2OH

2) H3O+

(77%)

,
: '
1

R COOR

LiA lH4 -BF3

R C H2O R 2

O
H2C-(CH2)n-C
O

1) LiAlH4,
+
2) H3O

H2C-(CH2)n-C
O

(50-80%)

-
-(-) LiAlH[O(CH3)3]3

.18 (.).



.
, ..
.
1306

1307

- .
4--
, 4--:
H

O
1) LiAlH4,
+
2) H3O

(CH3)3C

OH
H

OH + (CH3)3C

(CH3)3C

(20%) -

(80%) -

, -
-
, -
.

, ,
-:
CH3

CH3

CH3

CH3

1) LiAlH4,
+
2) H3O

CH3

(90%)

CH3

OH
CH3

CH3

H
CH3

(10%)

OH

, [2.2.1]-2()
-:

1) LiAlH4,
+
2) H3O

H
(89%)
-

OH

OH
(11%)
-

,
.
,
. (1952; . .8).
,

1307

1308

.
- RMgX RLi
,
,
- .
,
.
:
R

O
C C

R
R

R1

+ R MgX

C C R
R OMgX

R; R,; R - ,
.

:

R1

OH

R1(H)

R (H)

OH
R

OH

3--2
:
H
CH3CH2

C C
C6H5

O
CH3

1) LiAlH4,
+
2) H3O

H
CH3CH2

OH
C C H
C6H5 CH3

-.
,
, :

1308

1309

C2H5
O
H

OH

CH3CH2

C6H5

1) LiAlH4,
+
2) H3O

CH3

C6H5
CH3

CH3CH2
+
HO

C6H5
CH3

(75%)

(25%)

, -,

,
, .
(-, - - )

(CH3)2C=CH(CH2)2CH=CH-C

O (CH ) CHOH; Al O
32
2 3
H

CCl4

(CH3)2C=CH(CH2)2CH=CH-CH2OH + (CH3)2C=O
(88%)

-
-, -
.
- -
:
R

Al O
C O +

C
H

CH3
CH3

CH3
R
H
C
R C
CH3
O
O
Al
(CH3)2CHO
OCH(CH3)2

CH3

C CH
R C
3
O
O

Al
(CH3)2CHO
OCH(CH3)2

R2CHO Al

OCH(CH3)2
OCH(CH3)2

+ (CH3)2C=O

, .

, ,

1309

1310

.
,
-
.
,
.

.

.


.
(1913).
, - (.13).
O
C

(CH2)3CH3

Zn(Hg)
HCl; H2O; to

CH2(CH2)3CH3
(88%)

O
C

(CH2)5CH3

Zn(Hg)

CH2(CH2)5CH3

HCl; H2O; to

OH

OH

(85%)

,

- .
,
:
O
C

(CH2)16CH3

Zn(Hg)
HCl; H2O; to

1310

CH2(CH2)16CH3
(77%)

1311

, :
O

Zn(Hg)
HCl; H2O; to

H
(75%)

,
:
CH3(CH2)5C

O
H

Zn(Hg)
HCl; H2O; to

CH3(CH2)5CH3
(72%)

.
16.3.7.

,
, .
. 0-20
,
80%:
CH3(CH2)4C

O
H

O
CH3(CH2)3CHC H
CH2CH3

CrO3-H2O-H2SO4
; 0 oC
KMnO4
H2O; KOH; 0 oC

CH3(CH2)4C
(85%)

O
OH

O
CH3(CH2)3CHC OK
(78%) CH2CH3

,
,
- .
- ( ).
- ,
.:

1311

1312

Ag2O
-

CHO

(86%)

COOH

CHO

COOH

Ag2O
-; 20
(97%)

H
CH3CH2

C C

CHO

Ag2O

CH3

H2O; NH3

H
CH3CH2

C C

COOH
CH3

(98%)

(
).
, -,
, :
O

OH
R C OH
H

+ HOH

R C
H

, ,
(1,1-) rO3
.
, :

O
R

OH
CrO3

+
R C
H ; H2O
H
HO

+ HOH

CrO 3H

R C
HO H

O
R

C
H

+ HCrO 3

,
nO4
.
, ,
:

1312

1313

O
COOH COOH
CH2
(80%)
CH2
KOH; H2O; t o
CH2 CH2
KMnO4

16.3.7.. (
-)

,
, nO4; N3,
:
C CH3
C6H5CO3H
O
CHCl3

O C CH3
O
(67%)

, . . 1899
., : ,
e, .
90%-
- :
O
O
(CF3CO)2O-H2O2
CH
CH
-O-C-CH
CH3CH2-C-CH2CH3
3
2
2CH3
CH2Cl2
(78%)

90%-
:
O
CH3(CH2)5-C-CH3

BF3-H2O2

O
CH3(CH2)5-O-C-CH3
(60%)

,
:

1313

1314

OH
R C O O

R C R + CF3CO3H

O
OH

O
C CF
3

R C OR + CF3CO2

RC
OR

+ CF3COOH

, .
,
, ,
.
> 65 > (3)3 > (3)2 > RCH2 >>
3. ,
,
. .
-
. ,
- :
O
O
CH3COOC2H5 O
+ CH3CO3H

-
(90%)

O
O

O -

BF3; H2O2
CH2Cl2

(70%)

-
:
SeO2

6H5COCH3

CH3COOH

C6H5COCHO + Se + H2O
(72%)

SeO2
CH3COOH - C6H6

1314

(60%)

1315

,
:

O
(CH3)2S
C CH2Br

Br2
Ar
ArCOCH3
CH3COOH

Ar

CH3

CH3
C C H Br
O H

O
ArC C

+ (CH3)2S + HBr

,
, -
-:
O2N

1) Br ; CH COOH

2
3
COCH3 2)

O
C C
H
O

O2N

(72%)
n-

16.3.7..

.
Fe(II)
.
.

[RC=] ,
:
O

R C

R C

+ OOH

H

-
:
O
RCHO +

R C

O-O

+ OOH

R3,
:

1315

1316

O
+

R C

O-O

R C
O-O

O
R C

R C

+ R C

R C
H

O-O

RCO3H + R C

O-O-H
O

O
2R C

OH

,
-
.

[C6H5C=O] [RC=O] .
, , ,
.

. ,
( - ),
. , , ,
:
OH

+
COOH

CHO

OH

OH

H2O2

H2O2-H2O
H2O2-NaOH
H2O2-CH3COOH

70%
0%
0%

OH

100%
100%

,
.
.
-

1316

1317

(. 16.5) -
-

C6 H5C

ArCHO

Ar

OH

O-OH

Ar

HCOOAr

H2O

ArOH

C H
C C6H5

O O

ArCOOH

16.5

CHO

C6 H5C

COOH
+

O-OH

80% CH3OH-H2O

X
X-

OH
X

ArOH

ArCOOH

rO

r rO

n-

94

92

91

99

95

98

n-

69

17

40

19

73

39

37

68

100

90

90

n-l

93

97

n-NO2

100

98

-NO2

98

(, ,
.).
,
- -
:
CHO
OH
CH3O

3%- H2O2
NaOH; H2O; 50 oC

OH
OH
CH3O
(80%)

1317

1318

CHO
OH

OH

3%- H2O2
NaOH; H2O; 50 oC
20

OH
(100%)

16.3.8.

-
1853 . ..
, - ,
-

.
.

R3:
2ArCHO
2R 3CCHO

CHO

HO

KOH
-

ArCH 2OH + ArCOOK

KOH
-

R 3CCH 2OH + R 3CCOOK

50%- KOH
-
100 oC

CH2OH +
(94%)

HO
2 C6H5CHO

50%- KOH
-
20 oC

COOK

HO

(94%)

C 6H5CH2OH + C6H5COOK
(85%)

(85%)

,
.
R3C
, ,
:
KOH
-

ArCHO + H CHO
O
CH3

CHO + HC
H

KOH
C2H5OH

A rCH2OH + H COOK

CH3

CH2OH + HCOOK
(90%)

1318

1319

. ,
-,
-, .
, :
O
H
O

O
C
H

C H

OH

CH2O

C
OH

OH
O
C
O

CH2OH
+

,
: v =
K[r]2 [-].

-, .. v = K[]2 [-]2.
, -
,
.
-
, -
:
O

ArC

OH

O
Ar

OH

C H

+ ArC

Ar

C
O

OH
ArCH2O

O
O

1319

Ar

H
:H + H2O

1320

, -
. D2O
, C6H5-CDO
65D2O. , -, ,
- ,
- .

()2 >> ()2 > LiOH > NaOH >> R4N+OH-.
, -
,
.

ArCHO

MOH

ArCHOM

ArCHO

Ar
HO

OH
ArCOOH + ArCH2OM

O
C

M
H

O
C Ar
H

ArCOO M + ArCH2OH

18--6-,
.
- ,
.
.
16.3.9.

,
- [(65)3]3RhCl:
RCHO

[(C6H5)3P]3RhCl

RH + RhClCO[P9C6H5)3]2 + Ph3P

(I) 20 o,
.

1320

1321

,
- :
CHO
CH3

C C2H5
Ph

[(C6H5)3P]3RhCl
C6H5CN
110 oC

H
CH3

C C2H5 +
Ph

+ RhCl(CO)[PPh3]2 + Ph3P

(III),

.

RhCl[PPh3]3

Sol

Sol
Rh
Cl

PPh3
PPh3

OC Cl PPh3
Rh
R H PPh3

RCHO

RCO Cl PPh3
Rh
Sol H PPh3

RH + RhCl(CO)[PPh3]2 + PPh3

1321

1322

17
-
17.1. -
.............................................................................................................................. 1322
17.1.1. . ............................ 1322
17.1.2. .............................................................................................. 1327
17.1.3. Ke- ....................................................................................... 1328

17.2. ................................................ 1332

17.3. - ............................................... 1335
17.3.1. - ..................................................................................... 1338
17.8.2. -..................................................... 1341
17.3.3. - ....................................................................................... 1346
17.3.4. - ........ 1348
.............................................................. 1354

17.5. C - ............................ 1361

17.5.1. ............................................................................................. 1361
17.5.2. ........................ 1370
17.5.3. ............................................................................................... 1376
17.5.4. ........................................................................................... 1378
17.5.5. ........................................................................................................... 1382
17.5.6. ........................................................................................... 1385
17.5.7. - ................................ 1390

17.6. - .......... 1393

17.7. ........................................................................... 1396
17.8. 1398

17.1. -

17.1.1. .

-
.
,
, , .
.

1322

1323

O
C CH3 + Br2 CH3COOH
50 oC

Cl

O
C CH2Br

Cl

(77%)

Cl
HCl; H2O

O + Cl2

O (66%)

20 oC

Cl

CH3
O + Cl2

CH3

CCl4-CH3COOH

(85%)

,-

. , , 2--2--
2--2-
E2-.

Br

CH3

CH3
O

C5H5N; t o

(62%)

, ,
ore ,
.

, -
, . , oe
,
.

-3,

-,

2-

. , ,

,
- ,
.

1323

1324

.
, ,
- .
CH3

CH3

D2O; D

O + H2O
D

.
, - - C6H5OC*H(3)-C23 ,

- .

, 3--2-
C6H5OC*H(3)-C3 .
, pea
,
,

,
,
.
R- S- .
-
,
.

1324

1325

O
(R)-CH3CH2C*H C
C6H5

CH3

OH

CH3CH2C

CH3 C6H5
()

I2

(S)-CH3CH2C*H C

CH3CH2C
C6H5

CH3

D2O

CH3CH2C

O
C

CH3 C6H5

CH3 C6H5

- .
1- .
1

H
R C C R2
OH H
1

R C CH2R + HA
O

R1 C CHR2 + HA
OH

,
. ,
,

.
H

O
C C

Hal

OH
C C

OH
C C + Hal

OH

-H

C C

Hal

Hal2

O
C C

+ HHal

. ,
-- . , ,
- . ,
, ,
.

1325

1326

-,
,
- .
O

B ;

(R)-CH3CH2C*H C
C6H5

CH3

BH;

HB;

O
C
CH3 C6H5

CH3CH2C

- ()
B ;

Hal2

O
(S)-CH3CH2C*H C
CH3

C6H5

Hal
CH3CH2C

O
C

CH3 C6H5

D2O

D
CH3CH2C

O
C

CH3 C6H5

-
.
, ,
.
,
.
, .
-
. -
. ,

.
. -
-
,
-.

1,1,1-,

1326

1327

O
RCCH3

I2; NaOH
H2O

O
NaOH

RCOO

C CI3

CI3

+ CHI3

OH

.
.

. I3
.

17.1.2.

,
, ,
.
.
O
1

R C CH2R

OH
2 HNO2

R C CHR

O N=O
1

R C CHR2

O N-OH
1

R C CHR 2

().

-
. -O
, .
O

O
1

R C CR 2
N OH

Zn
CH3COOH

R C CHR 2
NH2

. ,
1,2-.

1327

1328

O
C6H5

O N OH
C5H11ONO
CH2CH3
HCl

C6H5

C C CH3
(65%)

H2SO4
H2O

O O
C6H5

C C CH3
(70%)

17.1.3. Ke-

.

. : ,
, -
.

8.10-6
% 10-4 % oe . ,
- , .
, , , -H .

, ..
. -H
-, .

. , , F3COCHF2
-
100 .

OH

CF3 COOH
CF 3C=C F 2
100 o C

C F 3 C-CHF 2

,
:

1328

1329

F F F F

F
F
OH

F
F

F F F F
F
F

F
F

99,9%

0,01%

,
, ,
-.
OH

HCl; 60 oC

MesC=C-Mes

CH3OH

CH3

O
Mes-CH-C-Mes
CH3

CH3
Mes = CH3

CH3

. Mes2C=C(OH)Mes
.
1,3-
1,3-.
80%, 8%.
, ,
.
, ,
.
CH3

C CH2 C CH3
O

H3C

CH3

80%

C CH2 C OC2H5
O

20%

CH3

H3C

92%

C
8%

1329

O
OC2H5

1330

. 1,3 1,3-
.

. -, , .
23% 6%
. ,

-. , . 17.1


1,3- .

. HCl
-78 oC.

-78.
.

1,3- 1,3-.
17.1.

- 1,3- , =
[]/[]

[]/[]

10

-5

10

-3

10-6

8 10-8

1330

1331
.

10-6

10-5

10-4

10-5

7 10-2

50

-3

2 10-8

1 10-7

5 10-6

2 10-7

2,3 10-1

80

23

90

20

100

98

100

-1,3

,
. -
-
900 .
HOCH2CH2OH

900 oC
CH2=CH
0,02 ...

+ H2O

OH

80 25
,
.
,
.
119,3 o

1,332 A

1,078 A
o

1,090 A

123,5 o
o

121,5 o 126 o

1,079 A
o

1,373 A

O
o

0,956 A

-2 .
O
CH3-CCH2CH2CH3

OH
h

CH3-C=CH2 + CH2=CH2

.
-
3 5.10-8, 8.10-8.
1331

1332

, - 12-14 /
. 1,3, .

17.2.
,
-, ,
C-H -o -
.
- - sp3
sp2, - -

. -
- ,
,

, -.

C
O

()

C
O

sp2

sp3

C
O

- G0

.
-
- ( 18). -
, , ,
O- .

1332

1333

- - -. 17.2
, ,
, 1,3- .
17.2

- --

1,3,5-

(3)3

5,0

1,3-

323 ()

9,0

1,3-

3225 ( )

10,7

1,3-

CH2(CN)2 ( )

11,2

1,3-

CH2(COOC2H5)2 ( )

13,0

CH3C(O)Cl ( )

~16

CH3CHO ( )

~18

CH3COCH3 ()

~20

CH3COOCH2CH3 ()

~25

CH3CN ()

~25

N,N-

CH3CON(CH3)2 (N,N-)

~30

, . 17.2, ,
, , ,
.
- N,N-
- . , 1,3-
, . 1,3 ( =
15,7) ( = 16). - 1,3-
, ,
, .
O

O
B

CH3CCH2CCH3

BH + CH3-C-CH-C-CH3

O
CH3C=CHCCH3

CH3CCH=C-CH3

, , , N,N-
- .

1333

1334

. -,
, 32O- ( = 16),
~0,01% - ~20.
O
CH3CCH3 + C2H5O

CH3C

O + C2H5OH

~99,99%

~0,01%

-
, NaH, KH, (C6H5)3C-Na+
- , , .
-
() Li+N(C3H7-)2- , ()
.
CH3
[(CH3)3Si]2N Na

CH3
O

O
LiN(C3H7-)2

Li
+ HN(C3H7-)2

- -78
pKa~20

100%

NaN[Si(CH3)3]2

-78

CH3CCH3

CH3
N Li
CH3

CH3C
O

pKa~40

O + HN[Si(CH3)3]2
Na

100%

-78

CH3COC(CH3)3 + LiN(C3H7-)2
-
CH2

Li

OC(CH3)3 + HN(C3H7-)2
100%

- .

1334

1335
-78

(C3H7-)2NH + -C4H9Li -

LiN(C3H7-)2 + C4H10

, .
,

N,N-,

-78 ,
N(37-)2 =40.
() , .

. , -
-78
-.

-78

CH3COC(CH3)3 + LiN(C3H7-)2 -
pKa~25

CH2

OC(CH3)3 + HN(C3H7-)2
pKa~40

O Li

.
- , ,
.
, .

17.3. -
-

16 :
, . ,
,

.
-.

1335

1336

(.., .., ..):
1) ,
2) ,
3) -,
4) -,
5)

-,

..

/-

,

- -,
.

- , 1,3- 1,3 , ,

, - . ,

(NBS,

),

RSCl, RSBr, RSeCl; +, FClO3;

, .

oe, ,
(RO)2l, RSO2Cl, .
.
O

1) ; ; -78
2) (H3)3SiCl

OSi(CH3)3
99%

16

(.) -
1336

1337

CH3CH2CCH2CH3 1) [(CH 3)3Si] 2NNa; -78 C H3CH2C=C HCH3

2) (H 3CO) 2O

CCH3

100%
1) ; ; -78
2) NBS

O
83%

Br

C 6H5SSC 6H5 + C l2

2C 6H5SCl

O 1) ; ; -78

2) C6H5SCl

86%

SC6H5
1) ; ; -78

O 2) C6H5SeBr

89%

SeC6H5

-.

-
C6H5SeOH a,b .
, , , .

-,

, .
H

H
C

O
C
R

1) ; ; -78
2) PhSeBr; -20 oC

Se

H
C

C
O

O
H2O2
20-60 oC

SeC6H5

C6H5
C

20-60 oC

C
O

O
c-

1337

R + C6H5SeOH

1338

,-

,-

.
O

O
1) ; ; -78
2) PhSeBr; 3) H2O2

55%

,-
.
O
1) ; ; -78
OCH3 2) PhSeBr; 3) H2O2
1) ; ; -78

CH3(CH2)4CH2C N 2) PhSeBr; 3) H O
2 2

O
C OCH3
(96%)

CH3(CH2)2CH=CH2C N
(80%)

17.3.1. -

- , , 1,3- 1,3 .
- . SN2
,
, . - O -
RX. ,
-.

""

(ROSO2CF3) . ,
- , -

1338

1339

, 1,3- 1,3-. . 17.3

- O
.
O
1

R C

CHR + AlkX

2
1
2
R C CHR + R C CHR

OCH2CH3

R
O

OAlk

Alk

Alk
+ AlkX

RC CH COCH2CH3 +

OCH2CH3

AlkO

O
--

H
R
O

R
C

Alk
O

+ AlkX

RC CH CR +

+
AlkO

R
C
H

O
--

, .17.3, ,
- O- .
-
, O-.
CH3
O

C
H

OC2H5
O

+ CH3X

20 oC

CH3

CH3

CH3C CH COC2H5 +
CH3O
O
O
C-
X=I
X = OTs

1339

97%
3%

C
H

-
3%
97%

OC2H5
O

1340

o
(CH3)2CHCCCH(CH3)2 1) KH; ;o-78 C
2) CH3I; -78 C

(CH3)2CHCC(CH3)3
O

98%

17.3

- O- , 1,3- 1,3-

/-

C6H5COCH(C3)CH3

Na ;

3I

0,0 ( C-)

-"-

CH2=CHCH2Br

0,0 ( C-)

-"-

Na ;

C2H5Br

0,61

-"-

-"-

C2H5OTs

2,4

CH3COCH2COOC2H5

+; T

C4H9OTs

9,0

-"-

-"-

CH3OTs

8,1

-"-

-"-

CH3Br

0,16

-"-

-"-

CH3I

0,05

-"-

-"-

CH3CH2Cl

1.5

-"-

-"-

(3)2l

4,3

-"-

-"-

(3)2r

2.2

-"-

-"-

CH2=CHCH2OTs

0,28

-"-

-"-

2=2r

0,0

-"-

-"-

CH2=CHCH2I

0,0

CH3COCH2COOC2H5

+; A

(CH3)3CCH2Cl

100

-"-

-"-

CH3OCH2Cl

100

-"-

652l

0,06

N (C4H9)4; CHCl3

CH3I

0,01

Na ; A

652Br

0,0 ( C-)

-"-

N+(C4H9)4;

CH3Br

0,0 ( C-)

-"-

-"-

BrCH2COOCH3

0,0 ( C-)

-"-

-"-

C4H9Br

0,0 ( C-)

(CH3)2CHCOCH3

Li+;

652Br

0,0 ( C-)

-"-

-"-

32r

0,0 ( C-)

-"+

-"CH3COCH2COCH3

, - ,
- -.

1340

1341

- - ClCH2OR, ClCH2NR2
- .
-
, . -
, ,

s3- s2,

O-.

O-.

, O/- ,
.
- .

17.8.2. -

-.
, ,
,

-.

.
1

RCH2

C CH2R

LiN(C3H7-)2
; -78 oC

RCH

C CH2R

+ RCH2

CHR

O Li

O Li

-78 oC (CH3)3SiCl

-78 oC (CH3)3SiCl

RCH

C CH2R

OSi(CH3)2

RCH

C CH2R

OSi(CH3)2

,
,

1341

1342

.
.
1

RCH2

C CH2R

RCH

C CH2R

+ RCH2

O Li
(CH3)3SiCl

RCH

CHR

O Li
2

C CH2R

+ RCH

C CH2R

OSi(CH3)2

OSi(CH3)2

LiN(C3H7-i);

LiN(C6H11)-C3H7-i; [(CH3)3Si]2NLi;

CH3
Li N
CH3

CH3

CH3

(, , ) (-78 )

.
, , ,
. -
,
O-

. , . 17.4,

,

,
, -.

.

1342

1343

-.
17.4

- .

, %

28

94

72

25

87

75

13

99

10

66

90

34

98

CH3

CH3
O

CH3
O

H3(CH2)4COCH3

O
CH3(CH2)3CH

C CH3

O
CH3(CH2)4 C

(CH3)2CHCOCH2CH3

CH2

O
(CH3)2C

C CH2CH3

O
(CH3)2CH C
O

O
C6H5CH2

C CH3

CHCH3

(C6H5CH

C CH2CH3

O
C6H5CH2 C

CHCH3

1343

1344

, , . ,

.

,
-78 .
-
-
, -.

CH3

1) LiN(C3H7-i)2; , -78 oC
2) CH3I; 20 oC

CH3
CH3

O
30%

CH3
O

O Na

CH2 CH=CH2

CH=CH2
+
CH2
CH2
CH3
CH2=CH

+
O
50%

35%

C(CH3)3

C(CH3)3

CH2=CHCH2Br

CH3

CH3

CH3

70%

C(CH3)3

C(CH3)3

CH3
O
15%

o .
ON(C4H9)4
CH3

OSi(CH3)3
CH3 N(C H ) F
4 94

O
RBr

CH3
+

80% -

O
R

CH3
R = C6H5CH2; CH2=CHCH2;
-C4H9; CH2C(O)OEt

+
20% -

,-.

1344

1345

.
1

R CH

O
O
2
C R + R1 CH C R2

R C

O
1

O
2

C R

Alk

Alk

O
1
C R2 + R CH2

Alk
1

R + AlkHal

O
2
C C R

Alk

Alk

, -
.
CH3C

CHCOOC2H5 + CH2=CHCH2Br

20

O
CH3

CH2CH=CH2

O
C CH C OC2H5 + CH3

C C COOC2H5

O CH2CH=CH2

O CH2CH=CH2
52%

48%

(,

, ,
,- .

,-.
-
. 1,3- : 1,3- 1,3 -
"" ,

, 1,3-
- . ,
, - o ~11, -

1345

1346

3- 20, ..
.
,

1,3-
-.
1

R COCH2COR

1) LiN(C3H7-i;)
2) AlkI AlkBr

R CCOCOR

O Alk

(CH3)3COK;

RCCH2CR
O

O
R

AlkOTs AlkOTf

AlkO

O
H

17.3.3. -

-

. ,

,
.
O
CH3(CH2)4CCH3

OCOCH3
1) KH;
2) (CH3CO)2O

CH3(CH2)3CH=C-CH3

-
- . , ,

,

- - 3:1.

1346

1347

CH3CH

(CH3CO)2O

C CH2CH3

CH3CH C CH2CH3

OCOCH3

O Na
(CH3CO)2O

O
CH3CH C CH2CH3 + CH3 CH C CH2CH3
OCOCH3

COH3
1

.
-30
, ..
.

-, -

.

C C
OCOR

C C

O C
O

.
CH3COCl

CH3

CH3

OCOCH3

100 %

CH2

O Na

C CH2

CH3COCl

CH3

C CH2COCH3 + CH3

C CH2

OCOCH3

79 %

1347

21 %

1348

17.3.4.
-

-
, ,
. , , ,

.
,
.
O
CH2

CH2 C C6H5

C C6H5
OSn(CH3)3

Sn(CH3)3

.
, Al3+ , R3Si+
,
g2+, R3Pb+ . .
R3Ge+ RnSn+
, .
,
.


.

(CH3)2CH C C(CH3)2
OMgBr

(CH3CH2O)2SO2

1348

O
(CH3)2CH C C(CH3)2
CH2CH3

73%

1349

O
CH3C CHC-OC2H5
OMgBr

(CH3)2CHCOCH3

(CH3)2CNH2

(CH3)2CHC CH2
BrMg

CH3OTs

CH3
CH3

CCHC-OC2H5
O

CH3
(CH3)2CHC

-CH3(CH2)3Br

NC(CH3)3

NC(CH3)3

65%

CH3MgBr

(CH2)4CH3

(CH3)2CHC

NC(CH3)3

H2O; H

(CH2)4CH3

(CH3)2CHC

80%

O
-
.

(CH3)2CH-CH

C CH3

(CH3CO)2O

O
COCH3CH3

OCOCH3

OM
M = Li
MgBr

+ (CH3)2CHCH C

(CH3)2CHCH CCH3

94%
48%

[Mg(O-C(O)-OCH3)2],

6%
52%

a C2 ,
- .
O
Mg(OCH3)2
1

R-CCH2R +
O

CO2

Mg(O-C-OCH3)2

Mg(OCOOCH3)2
120 oC

(MMC)

R C CH R1
HCl
O
C O CH OH
3
Mg O

O
R

C CH COOCH3
R1
1) Mg(OCOOCH3)2;
, 120
+
2) H3O ; 0 oC; H2O

COOH
91%

1349

1350

-.
.

, .

/O-

Li+ > Na+ > + > Cs+ > NR4+, ..
.

.
,
.
. ,
.
, , 0,1
11000,
40-50 .
, ,
. ,
.


.
Na+ +
18--6 .
,

.

.

1350

1351

-

-. ,

-,

.
, , -
1,3-

, .
CH3

CHCOOC2H5 + C2H5OTs

18--6

CH3COCHCOOC2H5

O K

CH3

CH3

OC2H5

C CHCOOC2H5
O C2H5

52%
C2H5
+
C CHCOOC2H5
48%

100%

, ,
N--2 -

.

,
-.

.
- - - 1,3 1,3-
.
-

. -

. -
1,3-

1351

1352

. ,
-.
,
- ,
.

,
.

CH3

CH3COCHCOOC2H5 + CH3

OC2H5

C2H5

CHCOOC2H5 + (H3CH2O)2SO 2

92%

C CHCOOC2H5

8%

CH3COCHCOOC2H5 + CH3
C2H5
15%

C CHCOOC2H5
OC2H5

85%

.
, - 1,3-
-
,
1-3%.
- , 1,3- 1,3-
-

- ,
.

. -,

1352

1353

CH3

CH2

LiN(C3H7-i)2
; -78 o C

C OC2H5

OC2H5 CH3(CH2)7Br

0 oC

O Li

O
CH3(CH2)7CH2

C OC2H5 + LiBr
O

(CH3)2CH C OC2H5

(CH3)2C

LiN(C3H7-i)2
; -78 oC

O Li

O
(CH3)3C

OC2H5 CH3I
-78 oC

C OC2H5 + LiI
O

CH3CH2

LiN(C3H7-i)2
; -78 oC

C OC2H5

CH3CH2

OC2H5 CH3CH2CH2C(O)Cl
-78 oC

O Li

O
CH3CH2

C CH C OCH2CH3 + LiCl
O CH3 O
79%

,-

,-.

-,

1,3-,

( 5.2 ).

(. ).

.

.

1353

1354

CH2

OC2H5 + CH2

0 oC

CH2
O

O Li

LiOCH2CH2CH2-C-OC2H5
O

O
-CH3CH2OLi

+ CH3CH2OLi

55% -

OLi

O
CH2

OC2H5 + (H3)3

C
H

O Li
OH
NH4Cl;
H2O; 0 oC

20 oC

(CH3)3C CH CH2 C OC2H5

(CH3)3C CH CH2 C OC2H5

97%

1,3-

, 1,3-
-
. -
-

.
.
1,3- : 32ON;
(3)3; N, , .

.

.
,
. SN2-,
, .

1354

1355

.
, , ,
,
, . ,
,-,

.

110-120

.
,
- .
CH2(COOC2H5)2
HCl ();
115 oC

1) C2H5ONa; C2H5OH
CH3(CH2)5CH(COOC2H5)2
2) CH3(CH2)5Br; 80 oC
90-95%

CH3(CH2)6COOH + CO2
75%

CH2(COOC2H5)2
HCl ();
115 oC

1) C2H5ONa; C2H5OH;
(CH3)2CH-C(COOC2H5)2
C2H5Br
2) (CH3)2CHI
C2H5

(CH3)2CH-CCOOH
C2H5

35%

,

.


.
.

1355

1356

COOC2H5
COOC2H5

1) C2H5ONa; C2H5OH;
2) Br(CH2)3Br

CH2(COOC2H5)2

COOH
1) KOH; CH3CH2OH-H2O
+
2) H3O ; t o

42-44%

N(C4H9)4+Br-
1,2-.
1)50%- NaOH-CH2Cl

CH2(COOC2H5)2 + BrCH2CH2Br

C6H5CH2N (CH2CH3)3Cl ;
+

2) H3O -H2O

COOH

120 oC

COOH + CO2

COOH

75%

70-72%

NCCH2(COOC2H5) + BrCH2CH2Br

1)50%- NaOH-CH2Cl
+

C6H5CH2N (CH2CH3)3Cl ;
+

2) H3O -H2O

CN
86%

120 oC

CN + CO2

COOH

77%

-
.
C H ONa

CH2(COOC2H5)2 + ClCH2COOC2H5 C2H5OH

2 5
HCl 115 oC

CH2COOH
CH2COOH

CH(COOC2H5)2
CH2COOC2H5

+ CO2 + CH3CH2OH

62%

, -
.
1) C H ONa; C H OH

2 5
2 5
CH2(COOC2H5)2 2) Br(CH
2)n COOC2H5

HCl 115 oC

CH2COOH

CH(COOC2H5)2
(CH2)nCOOC2H5

+ CO2 + CH3CH2OH
(CH2)nCOOH

1356

1357

. ,
, 1,2- - , 1,3 - ..
,-.
O
CH2Br2 + 2NaCH(COOC2H5)2

C2H5ONa
C2H5OH

HCl 115 oC

(CH3CH2OC)2CHCH2CH(COCH2CH3)2

HOOCCH2CH2CH2COOH

- -
,
.

- .
-

HCl

1,3-

.
O
CH3

C CH C OC2H5
R

HCl; t o

H2O

CH3

H
C

HO

CH3

C CH2R + CO2

O
CH3

C CH2R + CO2

. " " 1,3.
,
.

1357

1358

O
1) (CH ) COK;

3
CH3CCH2COC2H5 2) CH 3(CH
3
2)3Br

CH3CCHCOC2H5
(CH2)3CH3 82%

O
1) NaOH; H2O
+

2) H3O ; 20 o

CH3CCH2CH2CH2CH2CH3

65%

1) C2H5ONa; C2H5OH
CH3CCH2COC2H5 2) ClCH
2COOC2H5

CH3CCHCOC2H5
CH2COOC2H5

O
HCl . 100 oC
H2O

CH3CCH2CH2COOH 50%

O
C
OC2H5 1) C2H5ONa; C2H5OH

2) CH3(CH2)3Br

(CH2)3CH3
COOC2H5

O
48% HBr
H2O

(CH2)3CH3
60%

, ,
, () ,
, .
RX
-
.

CH3CCH2COOC2H5

2LiN(SiMe3)2
0-20 oC

Li CH2

Li

O
C

CH

1358

OC2H5

1359

Li

RBr

RCH2

H2O

RCH2CCH2COOC2H5

OC2H5

CH

CH3CCH2COOC2H5

1) NaH; C4H9Li
2) C2H5Br

CH3CH2CH2CCH2COOC2H5
84%

O
Li CH2

Li

R Br

Li

R CH2

OC2H5

CH
R Br

O
C

CH

OC2H5

R CH2CCHCOC2H5
2

,-
HCl :
1

R CH2CCHCOC2H5
2

HCl
H2O

O
1

R CH2CCH2R2

1,3-.

1359

1360

2LiN(C3H7-i)2

CH3CCH2COC2H5

Li

CH2

OC2H5

CH
O

CH2 CH2

COOC2H5

C O

CH2

Br(CH2)3Br

CH2 CH H

75%

Br
1,3-.
O

CH3CCH2CCH3

1) 2NaNH2
2) C6H5CH2Cl

CH3CCH2CCH2CH2C6H5
69%

-
.

,
. , , -

- .

CH3C=CHCOOC2H5 + (CH3)3CBr.AgBF4
OH

CH3NO2

O
CH3CCHCOOC2H5
C(CH3)3 68%

:
O
CH3C=CHCOOC2H5 + (CH3)2CH-O-BF3
OH

1360

CH3CCHCOOC2H5
CH(CH3)2 67%

1361

17.5. c -
17.5.1.

- (RCC-; CN-)
.
,
.
O

RCH2

+C

O
+

RCH

RCH2

OH

RCH2

C CH C
H

H R

OH
HOH

O
+ OH

C CH C
H R

- c (3-) ,
(-, -).
.

-, ,

- - 0-5 . ,
,
0-5 5 3--2- 55-60%
, 50%- .
CH3C

CH3H2C

O
H

+ CH3C

O
H

NaOH

HOH
0-10 oC
5

+ CH3CH2C

OH
CH3

NaOH

HOH
0-5 oC
5

C CH2 C
H

50%

OH
CH3CH2

C CH C
H CH3

55-60%

,- , .

1361

1362

CH3(H2)2CH2C

O NaOH

+ CH3(H2)2CH2C
OH

CH3(CH2)2CH2

HOH
H 0-5
oC

NaOH

C CH C

HOH
100 oC
3

H
H (CH2)2CH3
O

CH3(CH2)2CH2

C C C

86%

H
H (CH2)2CH3

O
2) RCH

H
O
3) RCH2

H R

+ H2O

O
RCH2

CH2R

O
+ HOH

C CH C

RCH

O
+

O
1) RCH2C H + OH

C CH C
H

H R

OH
RCH2

C CH C
H R

+ OH
H

-. -
1-3%,
17-18, 15,7. -

. ,-

- :
OH
RCH2

C CH C
H R

OH

OH
RCH2

C C C
H R

1362

O
+ HOH
H

1363

OH
RCH2

C C C

RCH2
H

H R

C C C

+ OH
H

H R

,
. , ,
:
OH

O
1) RCH2C H + HA

RCH C

OH
2) RCH C
H

3) RCH2

OH
RCH C
+ HA
H

+ A

O
+

OH

C H + RCH C

RCH2

OH

OH
O

C CH C
H R

OH

RCH2
H

C CH C
H

H R
H

C CH C
H R

H
O

4) RCH
2

+ A

+ H

RCH2

H
O

C CR C
H H

O
RCH2

C CR C
H

+ H2O + H
H

,
- .
,
.
,
- , -3
.

1363

1364

CH3

CH3CCH3 + CH3CCH3 () CH3

O
O

C CH2 C

80%

CH3

CH3
O

O +

C2H5ONa

38%

C2H5OH; t o

.
O
Na2CO3

96%

H2O; 20 oC

CH3
CH3C(CH2)4CCH3
O

KOH; 20 o C

C CH3
O

H2O

83%

. ,
,
. ,
, .
.
, ,
,
- .
C6H5C

O
H

CH3CH2C

Na2CO3

H2O; 60 o C

1364

O
C6H5CH C C
CH3

68%

1365

O
3 H C H + CH3C

Na2CO3

HOCH2

H2O; 40 oC

CH2OH
O
C C
82%
H
CH2OH

()

, .
O

OH

1)

+ C6H5C

NaOH
H2O

10 oC
5

CH C6H5

NaOH
25 oC
10

100%

O
CH C6H5
76%

2) C6H5C

CH3
3)

O
H

O
+ CH3CC6H5

CH3 O
O
C H
+
CH3CCH3

NaOH
20 oC
H2O

C6H5CH=CH C C6H5
85%

CH3
C2H5ONa
C2H5OH

CH3

CH3

49%

(, ) - -,
,
. .

.
-,
.
. ,
,-

1365

1366

.

, ,
(, .) 0-(-78)
.
[LiN(C3H7-i)2] LIN[Si(CH3)3]2 -78, ..
, .
, ,
,
- ,
.
""
,
.
1
O
R
3
2 CH C R
R

-78 oC

R1
C

Li
4

R
R

R1

O
H3
CH C CH3
CH3
1) CH3CHO; -78 oC
2) H2O-NH4Cl; 0 oC

O
4
5
R C R

OLi

H2 O

R3
4

OH

R
R

R3

CH3

LiN(C3H7-i)2,

-78 oC

CH3

O
C
2

OLi
CH C

CH3

CH2

O
CH C

CH3

CH2-CH-CH3
OH

75%

- .

1366

1367

H5C2
R1
C

OB(C2H5)2

H2 O

OH

R
R

C
2

R1

C
2

R3

OB(C2H5)2
+ C6H5
-C4H9CH C
C6H5
OB(C4H9)2

O
C CH C C6H5
H

C2H5

C6H5

R5

R C

R3

O
C

10
20 oC

HO

H2 O

C6H5

0-5 oC

C4H9

O
CH CH C C6H5

98%

C4H9

.
(-C4H9)3B + CF3SO3H

(C4H9)2BOSO2CF3 + C4H10
O

R CH2C

(C4H9)2BOSO2CF3 +

R2

R2

(C2H5)3N
-78 oC

+ CF3SO3 NH(C2H5)3

R CH C

OB(C4H9)2
-
,- . 16.
O
R3B + CH2=CH-C

RCH2CH=C

CH3

OBR2
CH3

TiCl4
-50 - (-78),

1367

1368

OSi(CH3)3

OH

+ C6H5C

O
H

OSi(CH3)3

+ C6H5CH2CH2C

CH C6H5

1) TiCl4; CH2Cl2; -78 oC

2) H2O; 0 oC

92%

OH

O 1) TiCl4; CH2Cl2

CH CH2CH2C6H5

2) H2O; 0 oC

70%

: ,
. , ,
, ,
:
CH3
CH3

C NC6H11 1) ; -78 ;
2) (6H5)2=O

SiO2
H2 O
25 oC

(C6H5)2C CH2 C CH3

OLi

(C6H5)2C CH2 C CH3

OH 64%

-, .

, .
R1
O

H
H

R
2

OM

R CH C
R1

H2 O

OH

R
R

O
+ RC

R1

H
R

1368

H2O

OH

R
R

1369

. Z- -,
- :
R1
R2
C
H

OM
C

+ RC

R1

Z-

O
1

H2O

OH

R
R2

R1
H
2

OM
C

C
R1

+ RC

H
H

O
1

H2 O

OH

R
R2

, , ,

. , , - Z-
-78 5-10

1369

1370

O
C

CH3CH2

C(CH3)3

(i-C3H7)2NLi;
; - 78 oC

C6H5CHO
; - 78 o C

C6H5

CH3

CH

C(CH3)3

OLi
OH

C(CH3)3

100%
-

CH3

Z-

Li-

- -,
- Z-.
CH3
O
CH3CH2C

CH3

CH3
LiO

(i-C3H7)2NLi;
; - 78 o C

CH3
LiO
CH3 + CH
3

H
CH3 CH3

C6H5CHO

C6H5

OH

O H3

CH3
H

- (92%)

; - 78 o C

CH3

CH3

Z- (8%)

O H3

OH
+
CH3

CH3
CH3

C6H5

CH3

CH3
CH3
- (8%)

- (92%)

17.5.2.

- . , -

, -
.
,

1370

1371

OR- (OC2H5-),
1,3-.
1) H3C

2) H3C

O
OC2H5

OC2H5

+
OC2H5 CH2

O
CH3

C OC2H5

H3CCH2C

OC2H5

OC2H5

C CH2 C OC2H5

OC2H5

OC2H5

C CH2 C OC2H5

4) H3CCH2C

C OC2H5 + C2H5OH

CH2

O
3) CH3

CH3C

OC2H5

CH2C

OC2H5

+ HOC2H5
OC2H5

, .
, ,

,
(11) , (15.9).
,
( = ~25) , .
C2H5OD, ,
50% 25 0,1
.
1887 .,
,
,
75%.

2 CH3COOC2H5

1) C2H5ONa; 8 ; 80 oC
2) CH3COOH-H2O

1371

O
CH3

C CH2 C OC2H5
75%

1372

,

, (1), (2) (3),

, (4).
R2CHCOOCH2CH3 ,
-, .
,
R2R223 "" 1,3- ~20.
,,
.
O
(CH3)2CHCOOC2H5

1) NaH; -
2) C2H5OH

(CH3)2CH C C(CH3)2 C OC2H5

58%

.
,
- ,
1,3-:
. ,

, ""

Ar23;

HCOOCH2CH3; (CH3)3CCOOCH2CH3.

. . (1894 )
150-170
.

1372

1373

O
C16H33CH2C

C OC H
2 5
C O
OC2H5

+
OC2H5

C16H33C

O
C OC H
2 5

C2H5ONa

150 oC

C16H33CH(COOC2H5)2 + CO

C C OC2H5

68%

O O

.
1) (i-C3H7)2NLi; ; - 78 oC

R1CH2COOC2H5 2) R2-C(O)Cl
O

R C CH C
1

O R

+ LiCl
OC2H5

60-80%

1,3-.
, - , .
RCH2COOC2H5
RCHCOOC2H5
SC6H5

1) (i-C3H7)2NLi; ; - 78 o C
2) C6H5S-SC6H5
1) (i-C3H7)2NLi; ; - 78 oC
2) C6H5S-SC6H5

SC6H5
RCCOOC2H5
SC6H5

O
HgCl2, HCl
CH3OH

C COOC2H5

1) (i-C3H7)2NLi; ; - 78 o C

RCH2H2COOC2H5 2) C6H5SeBr
RCH2CHCOOC2H5
SeC6H5

H2O2
to

RCH=CHCOOC2H5

.
, - .
1373

1374

(. 5.3).
2

R
O
O
1) (Si(CH3)3)3NLi; ; - 78 oC 3
C COOC2H5
R C H C COOC2H5
2) R2 -C-R3
1
OH R

R1H2

OH

1) (Si(CH3)3NLi; ; - 78 o C

CH3COOC2H5 2)

CH2COOC2H5

80-90%

, .,
:
(CH2)n

COOC2H5
COOC2H5

H2O-H2SO4; t o

NaH

(CH2)n-1

(CH2)n-1

C O
CH COOC H
2 5

C O
CH2

70-80% ,
, .. n = 4
n = 5. n
12
. 1,3- 14-16
30%.
.
, ,
1,3- ().
1

R CH2COR + R C OC2H5
O

1) C2H5ONa
+

2) H3O

R C CH C
1

O R

R2

-- 105 .
, -
. -

1374

1375

.

1,3- .
CH3 C OC2H5 + CH3 C CH3
O

CF3 C OC2H5 + CH3 C CH3

O

1) C2H5ONa
2) H2O-H2SO4

CH3 C CH2 C CH3

O

1) C2H5ONa

CF3 C CH2 C CH3

2) H3O ; 0 oC

O
38-45%

52%

:
O + HC

O
OC2H5

1) NaH,
2) H2O-CH3COOH

O
O

H
C

OC2H5
C O
OC2H5

O
C

1) C2H5ONa; C2H5OH; 20 oC
2) H2O-H2SO4; 0 o C

170 oC

O + CO
59%

COOC2H5

O
C
OC2H5

,
.
OC2H5

+ C O

ONa
NaH
; 110 oC

OC2H5

C OC2H5
O

O
CH3COOH-H2O
0 oC

94%

C OC2H5
O

1375

1376

17.5.3.

-

,
.

.
.. 1887 .

(, ) o.

.
3

R1CHCOOC2H5 + R C R + Zn
O

Br
OZnBr
2

R C CH C
R 3 R1

O H SO -H O; 0 oC
2
4 2

80 oC

OH
2

R C CH C
R 3 R1

OC2H5

OC2H5

60-90%.
CH3CHCOOC2H5 + C6H5
Br

C CH3
O

OH
C6H5

C CH C

80%

CH3 CH3 OC2H5

1376

1) Zn; ; 80 oC
2) H2O-H2SO4; 0 oC

1377

1) Zn; ; 80 oC
2) H2O-H2SO4; 0 oC

O + BrCH2COOC2H5
OH

71%

CH2COOC2H5
1) Zn; ; 80 oC
2) H2O-H2SO4; 0 oC

CH3(CH2)5 C H + BrCH2COOC2H5
O
CH3(CH2)5CH-CH2-C
OH

O
OC2H5

54%

,
, ,

0 .
, ,

BrZnCH(R)COOC2H5.

RCH=(OZnBr)OC2H5.

.
, .
2
R1 C R + CH2

OZnBr

OC2H5

O
Zn
O

Br
O

H ; H2O

C
R C
CH2
OC2H5
2
R

OH
2

R C CH2 COOC2H5
R

,
,

, - -,
1377

1378

,
.

17.5.4.

, .

,
, , -

, ..) .
. (1896 .).

C R + CH2
O

C
Y

+ H2O

Y = COOH, COOR, CN, NO2

,- , ,
(. 17.5).
17.5
, - , .

CH3(CH2)5C

O
H

+ CH2(COOH)2

; 100 oC

CH3(CH2)5CCH=CH-COOH + CO2 + H2O

79%

; CH3COOH
O + NC-CH2COOC2H5
; 80 oC

100%

O
C + CH2(COOH)2
H

CH=CHCOOH + CO2
80%

NO2

NO2

1378

COOC2H5

1379

100 oC

O + CH2(COOH)2

C H
C

91%

CH=CHCOOH

CH=CH2CN

+ NC-CH2(COOH)
N

O + CH2(COOC2H5)2

80%

; 100 oC

N
OOC2H5

; TiCl4

78%

COOC2H5

O
; CH3COOH
C + CH2(COOC2H5)2

CH=CH

COOC2H5
COOC2H5

O + CH2(CN)2

90%

; CH3COOH
; 80 oC

+ H2O

75%

CN

- ,
.

10-13 .
- 1820 .
.
.
CH2(CN)2; N223,
TiCl4.

1379

1380

. , ,
( )
,
.
-.
,- .
AcOH

C H + HN

N CHR OAc

CH2

X
Y

N CHR +

H
R CH C
NH

CH

+ HN

CH

H2N

X
R CH CH
Y
N

X
Y

+ HN

Y
X Y = COOC2H5; CN

X
Y

H 2N

+ HN

+ H2N

,
, , , -.
.
R
C
H

O + CH2(COOH)2

1380

R
H

O
C OH

C CH
O
OH C
OH

1381

O
C O

C CH
O
OH C
OH

O
C O

C CH
H
O
OH C
OH
H

C2H5NH

R
+ C2H5N

H
C C

+ CO2 + H2O
C OH
O

-
,- ,
.
,-
.

(1868

.)

170-200
.

ArC

O
H

RCH2

RCH2

O
O

170-200 oC
RCH2COONa

ArCH C

COOH
+ RCH2COOH
R

.
C6H5C

180 oC

CH3COOK
+ (CH3CO)2O (CH CO) O 8 6H5CH=CHCOOH
3
2
H
60%

O
C
H
OH

+ (CH3CO)2O

CH3COONa
175 oC

CH=CHCOOH
O
O-C-CH3

1381

+
O

1382

, -
.
:

CH3C

CH3COO
to

2O

CH3C-O-C

CH2
O

ArC

O
H

+ CH3C-O-C

CH2

O CH
Ar

ArCHCH2C
O CCH3

CH3C O

CH2

O
H O
(CH3CO)2O

Ar CH CH C O CCH3 + CH3COO
O CCH3
O
ArCH=CHCOOH + CH3COOH + CH3COO

(NO2, CN; Cl, r .)

, - ,
(3; 25; N(3)2) .
.

17.5.5.

. (1912 )
c

1382

1383

O
2

H C H + R2NH2Cl

R C CH2R +

1
RC
CH CH2 NR2 Cl + H2O

R2

, ,
, .
O
HCl
C2H5OH

O + H C H + (CH3)2NH
O

85%

CH2 NH(CH3)2 Cl

C6H5C

O
+ H C H + (CH3)2NH

CH3

C6H5C

HCl
C2H5OH
70%

CH2CH2-NH(CH3)2 Cl
O

O +

H C H
O

HCl

+ HN
O

O C H OH
2 5

100%

CH2 N
H Cl

,
:
O
H C H + R2NH
H + HOCH2NR2

HOCH2NR2

H2O CH2 NR2

CH2=NR2 + H2O

1383

1384

:
O
H C H + (H3)2NH

HBF4
CH2Cl2;
-20 o C

CH2=N(CH3)2 BF4

:
O

R C

H+
2

OH

CH2R
1

RC CHR

RC CHR + CH2=N(CH3)2

R2

RC CH + H
CH2N(CH3)2
O

OH

- .

.

.
(C4H9)3B + CF3SO3H

(CH CO) CO

(C4H9)2BOSO2CF3 N(C3H -i2) (C H )

3 7 2 2 5
84%

CH3CH2-C=CH-CH3 + CF3SO3 NH(C3H7-i)2(C2H5)

95%

OB(C4H9)2

CH3CH2 CH CH CH3 + CH2=N(CH3)2 CF3COO

OB(C4H9)2
CH3CH2C-CH-CH3 + CF3COOB(C4H9)2
O CH2N(CH3)2
.

1384

1385

1) CH =NR2X ; TiCl4; CH2Cl2

OSi(CH3)3 2) H O2
2
O

+ (CH3)3SiX

CH2NR2

2=NR2+X.

17.5.6.

, 1832
. . .
- ,
.

ArC

O
H

+ ArC

O KCN; C2H5OH
H

OH
ArCH-C-Ar
O

OH
O KCN; C2H5OH
+ C6H5C
C6H5CH-C-C6H5
C6H5C
- H2O
H
H
O 90%
O

-, .
-.

.
OH
1

ArCH-C-Ar + ArC
H
O

KCN; C2H5OH

OH

O
1
ArCH-C-Ar2 + ArC
H
O
1

1385

1386

2,4-

.
. ()
,
.
O

C6H5C

OH

O KCN; C2H5OH

+ n-(CH3)2N-C6H4C

C6H5CH-C-C6H4N(CH3)2-n

O 86%

,


- N+(C4H9)4CN- .
. ,
, 1904
:
(1) ArC

O
H

+ :CN

(2) ArCH

(3)

ArC

C N
OH

C N

ArCH

ArCH

C N OH

ArC

OH

C N
OH

CN H

+ O

+ ArC

H2 O

Ar

+ HOH

H2O

C C Ar

C N
+ OH
OH

CN H
Ar

OH O

C C Ar
OH OH
+ OH

CN H
(4) Ar

C C Ar

OH

Ar

C Ar

Ar

O OH

OH OH

CN H

C Ar + CN

O OH

-.

1386

1387

,

, -
.

() 1,2- c .
R1 C C R2 + Bi2O3

CH3COOH

O OH

C C R
O O

75-95%

- .
.
-
.

N-,

.
+

N C 12H25

2 CH3CH2CH2C

O OH

Br

N(C2H5)3

CH3CH2CH2C CHCH2CH2CH3
76%

, .
N-
- -2
: . -
N- 10
-2 .
+

N R

N R

B:

+ BH
S

1387

1388

N R

C O

N R

N R

BH

CHR1

CHR1

+ B:

OH

,
- ( ~ 10 ).
+

N R

N R
S
pKa ~ 10

+ B:

CHR1

OH

OH

+ BH

C OH

""

("") -
,
- -I .
, -.


.
+

N R
S

C OH

N R OH

H
1

C O
S

OH
+

N R OH
S

C CH R1 + B:
R1

OH

1388

C CH R1
R1

BH

1389

N R OH
S

B:

C CH R1
R1

O OH
1

O
C CH R1 + BH

OH

N R

BH

R C C R +

OH
O OH
1

R C C R +

N R
+ B:
S H

, -,
,
.
-
ArC-(OH)-CN.

,

""

. ArC-(OH)-CN ,-
, ,
(. 17.6).
ArC

O
H

+ CH2=CH-X

KCN N (C4H9)4CN

O
ArC

H2H2X

60-90%

X = -C(O)R; -C(O)OR; -CN

,
.
1,4-, -,
.

1389

1390

17.5.7. -

, ,
, .
, ,
, ,
.
Ar

Na K

C O

Ar

Ar
Ar

C O Na

- .
. -

1,2.
- ,
- .
- ,
- , , ,
-.
2

R
R

R
R

2+

C O

Mg
2
R
R

Mg

C O

R
R

OH

OH

2+

C O

Mg
2

Mg

H2 O

1,2-,
II.

1390

1391

,
.
,

1,2- , ,
.
O

(1) 2 RC

OC2H5

(2) 2 R C

C2H5O
(3)

+ 2Na

O
Na

O
Na

OC2H5
R

R C
R C

(5)

O Na
O Na

O
Na

R C

O Na

R C

R C

R + 2Na

OC2H5

Na C2H5O
C
R
OC2H5
O
Na
C

Na

(4) R C

2R C

OC2H5
R

R + 2C2H5ONa

O Na
O Na

1,2-
()

O Na

CH3COOH

R
R

C
C

OH
OH

C
H

OH

1903 .

1391

1392

RC

Na

O
OC2H5

; 0 oC; 3-5

R C CH R
OH

50-75%

, , ,
1947
(8-12)
, .

, .
,

- .

3000-10000 .

90-95%
.
2- 50%.

CH3O

(CH2)16 C OCH3

C O

Na

(CH2)16
; 140 oC

96%

C OH
H

O
C OCH3
Na
C OCH3 ; 140 oC
O

O
66%

OH
2-

-
.
,

1392

1393

-() ,
.
,

()

-
. 8-12

.
O
C OCH
C
3 Na; (CH3)3SiCl
(CH2)n
(CH
)
2 n
O

C
C
OCH3
O
C
+
Zn + CH3COOH
H3O ; H2O
)
(CH
2
n
(CH2)n

C
OH
H

OSi(CH3)3

OSi(CH3)3
C

O
n = 2-27

CH2

17.6. -

. -
1887 .,
.
C6H5CH=CHC

+ CH(COOC2H5)2
OC2H5
O
C6H5CHCH2C OC2H5

C2H5ONa
C2H5OH

72%

CH(COOC2H5)2
1,4- -
1,3-

:
1393

,-

1394

C CH2 C
O

R C
O

2
CH2 C R +

CH2 C

+ BH

C O
2
R

C C C R3

R C CH2 C CH C
O

B:

R3

BH

R C CH2 C CH C
O

C O
R2

R3

1,4- -
, 1,2 . ,
1,4- ,
1,2-.

-
( ) ,
, , , ,
.
- 1,3 - ; 1,3- 1,3 ( ) , 1,4-,
..
. - 1,3-
, , - ,

.
.
- ,- ,
.

1394

1395

O
CH3

C2H5OK
C2H5OH

+ CH2=CH-C-C6H5

CH3

-10 oC

CH2CH2CC6H5

64%

CH3
CH2(COOC2H5)2 +
C CH COOC2H5
CH3
CH3
C CH COOC2H5
70%
CH3 CH(COOC2H5)2

CH3

+ 2CH2=CH-C N

C CH2 C CH3
O

C2H5ONa
C2H5OH;
25 oC

NCCH2CH2 CH2CH2CN
CH3 C C C CH3

(C2H5)3N
C2H5OH

O
77%

C6H5

C CH2 C OC2H5+ C6H5CH=CH-C-C6H5

O

O
C6H5

C6H5

O
CH CH2CC6H5

C CH C OC2H5
O

C2H5ONa
C2H5OH

93%

O
C-OC2H5
+ CH2=CH2-C N

OH
N(C2H5)3CH2C6H5

O
C-OC2H5
CH2CH2CN
85%

- 1,3-
,
CH2=CHCN,

.
- . ,
, ,-

. - ,-

1395

1396

,
.

17.7.

, .
, 17
,

, . 1,5-

,
,
:
O
CH3
+ CH2=CH-C-CH3
O
C2H5ONa
C2H5OH
-10 oC

CH3

CH3

OH

CH3

C2H5ONa
C2H5OH
-10 oC

KOH
H2 O
100 oC

65%

C O
CH3

17

anula (.) -

1396

1397

O
CH3
O
CH3
+

O
CH3O

CH3O

O
CH3

O
CH3
1)
2)

O
HO

CH3O

, .
OCH3

OCH3

CH3CH2CCH=CH2

CH3ONa
CH3OH

O
OCH3

OCH3

1) CH3ONa; CH3OH

H3C

O
2)
CH3CH2CCH=CH2

- H2 O

O
H3C

OCH3

OCH3

CH3

CH3

- H2O
O

O
CH3

1397

(64%)

1398

17.8.

- .

.
-.

R2N

C C

C C

O
C

NR2

, . (1954 .)
, , - .
:
1) , (. . 16); 2) , -; 3)
1,5-.
- ,
.
- ,
, .
(3--2-), 1,5-.

n-CH3C6H4SO3H;
; 110 oC

O + HN

+ CH2=CH-C-CH3
O

+ H 2O

N
H2CH CCH3
O

H3O

H2O

H2CH2 CCH3

O + H2N
H2CH CCH3

1,5-

1398

1399

TiCl4
.
O

TiCl4
CH2Cl2
0 oC

R1 CH2 C R2 + 2R2NH

R CH C NR2 + R2NH2 Cl + TiO2

R2

,-
,- .
5-.
N

+ CH2=CH-C-OCH3
O

100 oC

H3O

H2 O

H2CH2 COCH3

O + H2N
H2CH COCH3
73%

- - - - .

CH2CH=CH2
+

CH2=CHCH2Br; CHCl3
60 oC

N
Br

CH2CH=CH2
+

H3O
H2O

H2N

66%

O
C(CH2)4CH3
N

CH3(CH2)4C(O)Cl; (C2H5)3N

CHCl3

Cl
C(CH2)4CH3
O

1,3-, 70%

1399

+ H2N

+ NH(C2H5)3Cl

H3O
H2O

1400

CH3CH2

O
N

1) BrCH2COOCH2CH3; ;

CH3 CH

2) H3O

80oC

CH3CH2

94%

C CH CH3
CH2 C O

-. ,
,
.

1400

OCH2CH3

1401

18.

18.1. ................................................................................................................ 1402
18.2. ....................................................................... 1407
18.3. .............................................................................. 1414
18.3.1. ......................................................................... 1414
18.3.2. ................................................................................................... 1415
18.3.3. ...................................... 1420
18.3.4. .
................................................................................................................ 1421

18.4. .................................................................. 1425

18.4.1. ........................................................................................................................... 1425
18.4.2. ................................................................................................................. 1428
18.4.3. , ,
, ........................ 1430

18.5. ......................................................................................................... 1433

18.5.1. ............................................................. 1436
18.5.2. . - . (1927 .)................................................................... 1445

18.6. ...................................................................................................... 1446

18.7. ................................................................................................................................. 1449
18.8. ............................................................................................................ 1451
18.8.1. ......................................................................................... 1451
18.8.1.. ......................................................................... 1451
18.8.1.. ..................................................................................... 1453
18.8.1.. -.......................................................................... 1454
18.8.1.. ................................................................................................... 1455
18.8.1.. ............................................. 1455
18.8.1.. ........................ 1456
18.8.2. ........................................................................................... 1457
18.8.2.. .................................................................. 1458
18.8.2.. 2 2............................................................................................. 1460
18.8.2.. L - .......................................................................................................... 1462
18.8.2.. 1............................................................................................................ 1464
18.8.3.. ........................................................... 1464
18.8.3.. ................................................................................. 1467
18.8.4. .......................................................................................................... 1468
18.8.5. ......................................................................................................................... 1469
18.8.6. ............................................................................................................. 1470
18.8.7. 1471

, .

1401

1402

H
C

H3C

O
H

=O

1.202

HC=O

124

=O

1.25

CC=O

119

1.343

OC=O

125

1.31

OC=O

122

OH

0.972

HCO

111

OH

0.95

CCO

119

HC

1.097

HOC

106

CC

1.52

, 120,
sp2- -.
p- p- -
, .
, ,
. ,
, .

O
2RC

O
R

OH

O
C

C
O

H o
2,67 A

14 /.

18.1.
.
, -
. .
18.1.

HCOOH

+8.5

+101

1.22

CH3COOH

+16.5

118

1.05

CH3CH2COOH

-21

141

0.99

1402

1403

CH3CH2CH2COOH

-6

163.5

0.96

(CH3)2CHCOOH

-46

154.5

0.95

CH3(CH2)3COOH

-34

186

0.94

CH3(CH2)4COOH

-4

205

0.93

CH3(CH2)5COOH

-7.5

223

0.92

CH3(CH2)6COOH

+16

240

0.91

CH3(CH2)7COOH

+12

254

0.90

CH3(CH2)8COOH

31.5

269

0.88

CH3(CH2)14COOH

64

390

0.85 65

CH3(CH2)16COOH

71.5

376

0.84 80

C6H11COOH

31

232

1.05

CH2=CHCOOH

13

142

1.05

CH3(CH2)7CH=CH(CH2)7CO

16

286

0.89

OH

HCCCOOH

18

144

1.13

C6H5CH2COOH

77

266

C6H5COOH

122

249

1.27 15

-CH3C6H4COOH

105

258

1.06 115

-CH3C6H4COOH

110

263

1.05 112

-CH3C6H4COOH

182

275

-ClC6H4COOH

242

1.54 24

- C6H4COOH

242

1.55 32

-HO-C6H4COOH

259

1.44 20

-H2N-C6H4COOH

246

(COOH)2

189

CH2(COOH)2

135

HOOC-CH2CH2-COOH

185

HOOC(CH2)3COOH

97

200/200

HOOC(CH2)4COOH

153

265/100

-HOOC-C6H4COOH

213

1.59 20

,
,
.

1403

1404

8
CH3

7
CH2

6
CH2

5
CH

3
CH

4
CH2

5
CH

4
CH

3
CH

CH3

CH3

Br

1
COOH

2
CH2

1
C

3--5-

OH

OH

CH3
6
CH3

2
CH2

3--4,5-

, , ..

-
2-

CH3CH2CHC
OH

Cl

O
CH3CH2CH2C

4-

OH
,
, ,

COOH

COOH

CH3

1-

Cl
COOH

1--2-

Br
18.2.

HCOOH

CH3COOH

CH3CH2COOH

CH3CH2CH2COOH

CH3(CH2)3COOH

1404

1405
CH3(CH2)4COOH

CH3(CH2)5COOH

CH3(CH2)6COOH

CH3(CH2)7COOH

CH3(CH2)8COOH

CH3(CH2)10COOH

CH3(CH2)12COOH

CH3(CH2)14COOH

CH3(CH2)16COOH

5.
= 4.74, 1% 0.1
. , Hl, HBr, H2SO4 .,
,
1011 .
-,
. -,
,

O
C

O
+

+H .

OH

-
, p- -
p- , p-
- .
-

O
R

C
O

O
R

1405

O.

1406
-.
- 1.27
= (1.20 ) (1.34 ) .
18.3 pKa 25.
18.3.

pKa 25

pKa

pKa

CF3COOH

0.23

-FC6H4COOH

4.15

CCl3COOH

0.64

-ClC6H4COOH

4.00

CHCl2COOH

1.26

-BrC6H4COOH

3.96

CH2NO2COOH

1.48

4.83

COOH
CF3SO2CH2COOH

1.88

CH3SO2CH2COOH

2.36

NCCH2COOH

2.47

HCOOH

3.75

CH2FCOOH

2.59

CH3COOH

4.74

CH2ClCOOH

2.86

CH3CH2COOH

4.87

CH2BrCOOH

2.90

CH3CH2CH2COOH

4.81

CH2ICOOH

3.18

CH3CH(CH3)COOH

4.84

CH2OHCOOH

3.83

(CH3)3CCOOH

5.03

C6H5CH2CH2COOH

4.66

CH3(CH2)6COOH

4.89

CH3CC-COOH

1.84

C6H5COOH

4.20

HCC-COOH

2.62

-CH3C6H4COOH

4.37

CH2=CHCOOH

4.65

-CH3C6H4COOH

3.91

CH3CH=CH-COOH ()

4.68

-CH3C6H4COOH

4.25

C6H5CH=CH-COOH ()

4.44

-IC6H4COOH

3.9

-CH3OC6H4COOH

4.08

-O2NC6H4COOH

2.17

-CH3OC6H4COOH

4.10

-O2NC6H4COOH

3.46

-CH3C6OH4COOH

4.50

-O2NC6H4COOH

3.43

-(CH3)3CC6H4COOH

4.20

C6F5COOH

1.75

-(CH3)3CC6H4COOH

4.38

2,4,6,-(NO2)3C6H2COOH

0.65

COOH

COOH

4.99

4.19

, 18.3, ,
.

1406

1407
50000 .
, , -
, , ..
pKa. -
, , pKa.
,
. -, -,
, , ,
, .

( 2). , -I-, , pKa .
.
, .
() .
2- (-) pKa 2.86, 3- () pKa 4.05; pKa 4- (-)
4.52, pKa (4.81).
, ,
.

18.2.
, ,
.
1) ( 11).

.

CH3CH2
CH3(CH2)3

CHCH2OH

CH3(CH2)8CH2OH

CrO3

KMnO4

H2O

CH3(CH2)3CH
H2SO4

COOH

74%

CH2CH3
CH3(CH2)8COOH 93%

2) ( 16).
, .
,-
.

1407

1408

CH3(CH2)5CHO
CHO
H

KMnO4 ; H2SO4
O
H2O; 20
Ag2O; KCN
H2O
CH2OH

CH3(CH2)5COOH

78%

COOH

Ag2O; KCN
H2O

78%

COOH
C

C
H

3) ( 16).
, , .

CHO

KOH
o
-; 100

OH

CH2OH

COOH +
OH

94%

OH

94%

4) ( -; 16)

.

CF3CO3H
CH3CH2COCH2CH3
CH2Cl2

O
CH3CH2OC
CH2CH3

NaOH
CH3CH2C
H2O

5) ( 17)

Br2 + NaOH
RCOCH3 - RCOONa + CHBr3
COCH3

COOH

NaOH; Cl2

- ; 70

+ CHCl3
87%

6) ( 5)
, ,
.
,
.
.

1408

O
ONa

1409

R1CH

CHR2

KMnO4; NaClO4
-

R1COOH + R2COOH

:
, .
, Mn+4
Mn+7. .

CH3(CH2)7C

C(CH2)7COOH

KMnO4; NaClO4
. - ; 10 O

CH3(CH2)7COOH + HOOC(CH2)7COOH
100%

100%

R1CH

CHR2

KMnO4

- ; 20

R1COOH + R2COOH

N(C4H9)4Br
CH3(CH2)7CH

CH2

KMnO4; N(C2H5)3CH2C6H5Cl
CH3(CH2)7COOH
-
91%

7) ( 12)
.
,

.
,
. .

1409

1410

CH3

O2N

KMnO4
; 100

CH3

O2N

COOH

88%

COOH

Na2Cr2O7

87%

CH3
CH3CH2

; 250

COOH

Na2Cr2O7; H2SO4
o
; 100

80%

COOH

18--6 .
0.06 ,
. .

CH3

KMnO4

COOH

; 18--6; 20

78%

8)
.

().

RCH

CH2 + CO + H2O

Ni(CO)4
RCH
o
200-500 ; 15.

COOH

CH3

.

.
9) ( 19)

CO2
RMgX

RCOOMgX

H2O
H+

RCOOH

, .

1410

1411

Mg

CH3(CH2)2CH2Br

CH3
H3C

CH3

Br

Mg

H3C

MgBr

CH3
Mg
(CH3)3CCl
(CH3)3C

CH

1) CO2
CH3CH2CH2CH2COOH
2) H2O; H+
73%

CH3CH2CH2CH2MgBr

CH3
1) CO2
2) H2O; H+

H3C

COOH

CH3
(CH3)3CMgCl
C 4H9Li

CH3C

1) CO2
2) H2O; H+
CLi

CH3
87%

(CH3)3CCOOH 80%

1) CO2
2) H2O; H+

CH3C

COOH 98%

.
10)

.
100-200 .

CH3

CH3

C6H5CH2C

CH2CN + KOH

o
200 ; 6

CH3

C6H5CH2C

CH2COOK

CH3
91 - 93%
75% - H2SO4

80%

150 ; 5
H3C

CN

CH3(CH2)15CN

H3C
KOH
o
CH3CH2OH - H2O; 100

COOH

CH3(CH2)15COOK 79%

.
.
-, 2
.

1411

1412

RCH2Cl

NaCN
o
; 100-150

RCH2CN

18--6
CH3CN

RCH2CN

RCH2Br + KCN

,
, ,
.
.
11) ( -)

. ,
.
,
.

RCOOH

SOCl2

O
RC

CH2N2

Cl
H2O

Ag2O

RC
CH

RCH

RCH2COOH

HOOC(CH2)8COOH

SOCl2
ClC
-

O
O

CH2N2
o
; 0-10

(CH2)8C

Cl
Ag2O
o
N2CHCO(CH2)8COCOHN2
-; 75
77%

HOOC(CH2)10COOH

72%

12)

. .

1412

1413

CH2(COOCH2CH3)2
. HCl
o
115

1) CH3CH2ONa; C2H5OH
o
2) CH3(CH2)6Br; 80

CH3(CH2)7COOH

CH2(COOCH2CH3)2

CH3(CH2)6CH(COOCH2CH3)2
90-95%

75%
COOCH2CH3

1) CH3CH2ONa; C2H5OH
2) Br(CH2)3Br

COOCH2CH3

COOH
1) KOH; H2O
+
2) H3O
42-44%

CH2(COOCH2CH3)2 + BrCH2CH2Br

COOH

50%- NaOH-CH2Cl2
C6H5CH2NCH2CH3)3Cl

COOH
75%

COOH + CO2

13) , , ,


.

.

.
o

NaOH + CO

200 ; 10 .

HCOONa

H2SO4
H2O

HCOOH

.

,
().

O
CH3C

+ O2
H

(CH3COO)2Co
o
80 ; 5 .

CH3COOH
90%

CH3CH2CH2CH3 + O2

Co(OAc)2
o

180 ; 50 .

1413

2CH3COOH
50%

1414


(. 28).

CH3OH + CO

o
"RhIII"; I ; 30 .; 180 C

CH3COOH

CH3OH
99%

18.3.
:
1)
2)
3) -
4) .
.

18.3.1.

. ,
.
.

CH3(CH2)7CH

CH(CH2)7COOH

(CH3)3CCOOH

LiAlH4
o
; 65

CH3(CH2)7CH

LiAlH4
o (CH3 )3 CCH2 OH
; 40

COOH(CH2)8COOH

LiAlH4
o
; 65

CH(CH2)7CH2OH
87%

92%

HOCH2(CH2)8CH2OH 97%

B2H6 .
CH2OH

(NO2; CN;

O
OR

),

1414

1415

O2N

1) B2H6; ; 20
CH2COOH
+
2) H2O; H

O2N

CH2CH2OH

1) B2H6; ; 20
CH3(CH2)4COOH
2) H2O; H+

CH3(CH2)4CH2OH

100%

18.3.2.
,
CO2
, .

-,
CCl4 .

RCOOAg + Br2

CCl4
80 O

RBr + CO2 + AgBr

CCl4
CH3(CH2)10Br + AgBr 67%
CH3(CH2)10COOAg + Br2
80 O
CCl4
CH3OOC(CH2)3CH2Br 68%
CH3OOC(CH2)4COOAg + Br2
80 O


.
, .
,
, . , ,
.

CH3(CH2)15CH2COOH

HgO; Br2
O
CCl4; 80

COOH + HgO + Br2

CH3(CH2)15CH2Br + H2O + CO2 + HgBr2

93%

CCl4
80 O

Br + HgBr2 + H2O + CO2

46%

- .

. CO2

1415

95%

1416
, ,
.
:

O
RCOOAg + Br2

+ AgBr

RC
OBr
O

RCOOBr

+ Br

RC
O

O
RC

+ CO2

O
O

O
..

RBr + RC

R + RC
OBr

. 1965 . ,

, .
, :

RCOOPb(OAc)3 + CH3COOH

Pb(OAc)4 + RCOOH
RCOOPb(OAc)3

R + Pb(OAc)3 + CO2

R + Pb(OAc)3

+ Pb(OAc)2 + CH3COO

, -,
-. -
.

1416

1417

COOH

Pb(OAc)4; LiCl
O
C6H6; 80

Cl + CO2 + Pb(OAc)2 + CH3COOLi +

+ CH3COOH

100%
O
C
O

Pb(OAc)4; C5H5N

+ 2CO2
[2,2,0]-2,5
( )

. Ag
Hg- ,

.
,
, ,
1849 . .
CH3, .

.. -
.

0-20
50-90%.

2 RCOO

-2eCH3OH

2 .C11H23COO

RR + 2CO2

-2eCH3OH - H2O

-C22H46 + 2 CO2
90%
-

-
10%.

ROOC(CH2)nCOOR n 2 34
.

1417

1418

-2eCH3OH

CH3COO(CH2)nCOO

CH3OOC(CH2)2nCOOCH3 + 2 CO2
40 - 95%
CH3OOC(CH2)8COOCH3

-2e-

CH3OOC(CH2)4COO

CH3OH; 20

75%

,
.

RCOO + CH3OOC(CH2)nCOO

CH3OH

RR + R(CH2)nCOOCH3 +
+ CH3OOC(CH2)2nCOOCH3

,
.

RCOO + CH3OOC(CH2)nCOO

CH3OH

RR + R(CH2)nCOOCH3 +
+ CH3OOC(CH2)2nCOOCH3

CH3OOCCH2CH

CH2COO + . C7H15COO

CH3OH

CH3
. C14H30 + CH3(CH2)7CH
49%

CH2COOCH3 +

CH3

+ CH3OOCCH2CH

CH2CH2CH

48%
CH2COOCH3

3%

CH3

. ,- ,-
.
,
: 1) - -

1418

1419

RC

O
O

; 2)

; 3) .

O
RC

-e-

O
RC
O

O
O
RC

R
O

R +R

+ CO2

RR

,
.
.

. XIX
.

O
RC
O

Ca

400

RC

+ CaCO3
R

RC
O
,
. -
, 380-4000.
.

O
2 RC
OH

ThO2 MnO
O
400

RCOR + CO2 + H2O

80%
250-300. .

1419

1420
-
. ,
(5%) 285-295 75-85%.
ThO2 c
20%,
.

18.3.3.

- 300-400 . , ,

, -
5%.

Cl2 + CH3CH2CH2COOH

h
O

300

ClCH2CH2CH2COOH +
31%

+ CH3CHClCH2COOH + CH3CH2CHClCOOH + HCl

5%
64%
.
,
.
- -, .
.

RCH2COOH + Br2

RCHCOOH + HBr
Br

--
, ,
.
, .
.
- .

1420

1421

2P + 3Br2

2PBr3

RCH2COOH + PBr3

+ H3PO4

RCH2C
Br

O
RCH2C

+H

RCH

RCH2C

+H
Br

Br

Br

RCH

OH

OH

O
+ Br

Br

+ HBr

RCH

Br

Br
Br
O

O
RCH

+ RCH2COOH

RCH

Br

O
Br

OH

Br

..

+ RCH2C

Br

, Pl3 PBr3.

H
COOH

+ Cl2

Cl

PCl3
O

170

COOH

+ HCl

94%
CH3CH2CH2CH2CH2COOH

PCl3; Br2
O

70

CH3CH2CH2CH2CHCOOH + HBr
83-89%

Br

- N- N-
,
- . -
,

18.3.4.
.
sp2-
- .

( ) (
) .

1421

1422
Z
.

O
RC

+ Nu

+ HNu

+Z

O
C

Nu

Nu

RC

RC

Nu

Nu

Z H

RC

Nu

+ HZ

Z = F, Cl, Br, I, OR, NH2, NR2 .

Nu

, .
Z -
. ,
, , ,
. ,

.
:

O
R 3C

O
< R2CH

O
< R2CH2C

< CH3C

O
R 3C

Cl

O
> RC

OC

O > RC
R

O
OR

> RC

NH2

.
G, , G,
. , , , ,
, C=

1422

1423

O
NH2

RC
: N > O > Cl.

O
OR
.

G 1, , , .

O
OR

. ,
, G2.
G3 . .18.1.?,

#
G1

RC

O
NH2

RC

1423

O
N H2

1424

#
G1

RC

O
NH2

RC

O
N H2

RC

O
O

#
G2

RC

O
OR'

1424

R'

1425

#
G3

RC

O
Cl

RC

O
Cl

.18.1. ,
. G1 > G2 > G3

, - -
, . ,
,
,
. , ,

. :
,
.

18.4.
18.4.1.

, . :
, , , , , , ,
.
,
:

1425

1426

H
C

CH3
=O

1.200

HC=O

124.95

O=O

1.334

OC=O

125.87

C(H3)O

1.437

HCO

109.18

O=CH

1.101

CH3OC

114.78

, - sp2O , - sp3O,
sp2O

, - , N
( 21).
.

O
C
H

H()
N

H()
=O

1.193

HC=O

122.97

1.376

HCN

113.23

HH

1.102

NCO

123.80

NH (a)

1.014

CNH (a)

117.15

NH ()

1.002

CNH ()

120.62

HNH

118.88

NH ,
.
NCO,
NR2 - N,N . NCO N,N N,N- 17.2-18 / (72-75
/).
nN-

n * .

,
- .

1426

1427
- -
, -60.

CH3

O
Cl;
:

O
C
H 3C

Cl
=O

1.192

CC=O

127.08

1.499

CCCl

112.66

CCl

1.789

O=CCl

120.26

CH

1.083

, CCl (1.789 )
CCl (1.784 ). ,
, , :

O
>

C
NH2

C
OR

O
> C
C1

CH3CN , :

Csp3

Csp

H
108

109.5

H
C
C
N
o
o
1.095 A 1.462 A 1.157 Ao

sp-

CN sp- .
sp3sp sp3Np -.
p- p -
. sp- .

1427

1428

18.4.2.

. ,
.

CH3CH2CH

(CH3CO)2O

CH2CH2

CH3

CH2CH2

CHCH2CH3
CH3

4-
,
.
.

CH3(CH2)9C

CH3(CH2)4C

Cl

, ,
.

O
CH3(CH2)4C

NH2

NH2

4-

O
CH3CH

CH3(CH2)7C
NH

CH2CH2C

N(CH3)2

CH3

CH3
4-

N,N-4-

1428

NH2

CH3

CH2CH2C

CH3CH

1429
,
, .
,
.

O
CH3C
OC2H5

COOC(CH3)3

CH3(CH2)4COOCH3

.-

.
, .., .

CH3(CH2)4CN

CH3CH

CH2CH2CN

CH3
4-

BrCH2(CH2)5CN

7-

CN
C6H5CN

CH3CH2CN

CH3
2-

. COOR ,

O
NH2

- ,

O
Cl

- , CN - .

1429

1430

H3COOC
H2NC
COOH

CHCH2C
CH2CH3

3-

Cl

3-

18.4.3. ,
, ,

,
- .

OH
RC

pKa

O
+H

RC
X

, ,

H 3O

, 1 = -5,2. ,

, .
sp2-
, sp3-
, .
,
.

1430

1431

H
R

sp3- ( )

+H

O +H

sp2- ( )

,
, . 18.4.
H3O+, CH3OH2+, R2OH+.
18.4.

0.0

CH3CONH2

OH
NH2

CH3C
H2O

-1.7

H 3O

-2.2

CH3OH

CH3OH2
CH3CH2OCH2CH3

-3.6

CH3CH2OCH2CH3
-6

CH3COOH

CH3C

CH3C

CH3C

O
OCH2CH3
O
CH3

OH
OH
-6.5

CH3C

OH
OCH2CH3
-7.2

CH3C

1431

OH
CH3

1432

CH3C

O
H

CH3C

O
Cl

CH3C

-8

CH3C

OH
H
-9

CH3C

OH
Cl
-10

CH3C

NH

,
,
. , :

O
R1 C

R1 C

+H
OR2

R2

,
,
.
.
-

O
RC

NH3

O
RC

RC

+H

NH2

NH2

. , ,
- sp- .
sp3- . N-H

1432

1433

NH4

( = 9,5)

NH

CH3C

( = -10)

C-H ( = 25) ( = 50),

.

18.5.

- : PCl3, PBr3,
PCl5, SOCl2 .
, - l
SOCl2 .

RCOOH + SOCl2

N(C2H5)3

+ HCl + SO2

RC

Cl

CH3CH2CH2CH2COOH + SOCl2

CH3(CH2)3COCl + HCl + SO2

87%
CH3

CH3
COOH + SOCl2

H 3C

C 5H 5N

COCl + SO2 + C5H5NH Cl

H 3C

CH3

CH3
90-95%

3 BrCH2CH

PBr3
CH2CH2COOH

BrCH2CH
CH3

CH3
3

COOH

PBr3

CH2CH2COBr + H3PO4
70%

COBr + H3PO3
90%

. RCOOH SOCl2 ,

-.

1433

1434

O
RCOOH + SOCl2

RC

O
O

+ HCl

S
Cl

OH

RC

O
O

RC

+H

Cl

Cl
H

O
RC
Cl

Cl

O
O

RCOOCl + HCl + SO2

S
Cl

. HCl
R3NHCl-. , -,
.
.
- ( 21).

O
+ SOCl2

HC

(CH3)2N

N(CH3)2

CH

S
Cl

Cl
O

(CH3)2N

CH
Cl

(CH3)2N
Cl

CH Cl + SO2
Cl

, ,
.

1434

1435

N(CH3)2

H
C
O
OH

N(CH3)2

+ HC

RC
OH

Cl

Cl
O

R
O

+ HCl

+ HC

RC

Cl

N(CH3)2

Cl

,
. , -,
- PCl3, PBr3, PCl5, POCl3 .
.
, ,
, , .
0-200 ,
, ,-
.

R
C
H

+ (COCl)2
COOH

0-100

R
C
H

+ CO2 + CO + HCl
COCl

1435

1436

O
O

+ ClC

RC
OH

- HCl

RC

OC

C
Cl

C
Cl

O
+ HCl

RC

+ CO2 + CO
Cl

- .

O
RC

+ COCl2
OH

- HCl

RC
O

O
+ CO2

RC

Cl

Cl

O
RCOOH + (C6H5)3P + CCl4

RCOCl + (C6H5)3PO

RC
O

P(C6H5)3 Cl

, (C6H5)3P
CCl4 ( 11).

.

18.5.1.

-
: , , ,
, , -, , - .
, - , OH-, OR-
sp2 - .
. . .
,

1436

1437
,
- .

+ HOH

RC

Cl

OH2

Cl

O
RC

RCOOH + HCl

+ Cl
OH2

. .
, .
, ,
.

O
+ (CH3)3COH

CH3C

C6H5N(CH3)2

Cl

+ C6H5NH(CH3)2Cl

CH3C

OC(H3)3
68%

O
+ CH3CH2CH2OH

C 6H 5C
Cl

C6H5OOCH2CH2CH3
86%
O

O
+

C 5H 5N
CH3Cl ; 200

OH

Cl

C 5H 5N
;

200

O
55%

, , ,
, ,

.

.

.

1437

1438
. . ,
N , .

CHCl3

(H3)2CHCOCl + 2 NH3

CH2Cl2

C6H5COCl + 2 NH(CH3)2
(CH3)3COCl + 2 NH2

(CH3)2CHCONH2

0-20

0-20

NH2

C6H5CON(CH3)2

CHCl3

(CH3)3CCONH

0-20

83%
92%
NH2

88%

,
,
.
.

O
RC

R1NH2

Cl

NH2R1

R1NH2

Cl
O
R1NH3Cl

RC
NHR1

0-50. .

-.
, .

H 3CO

H 3CO
H3CO
H 3CO

COCl +

NaOH
H3CO
- ;
0-50

H 3CO

HN

CO

1438

1439
,
.
, .

O
RC

O
+

CH2Cl2

- 300

Cl

Cl

RC
N

- ,
,
. ,
HCl , ,

O
RC

NR3Cl

-,

O
R 1C

O
R2OH

R 1C

O
N

R2

+ HN
OR2

R 1C

,
N,N- .
, ,
.
.

1439

1440

+ 2 HN

COCl2

N
N

N
N

N,N-
O
+

RC

N
N
N

OH

RC

CON

OC

+ HN

O
RCOONHR1

+ R1NH2

RC

HN
N

N
N
. .

,
-. RCOCl ,
- .

O
RC

O
LiAlH4

O
H

RC

Cl

RC

Cl

LiAlH4

Cl
O

RCH2OH

Cl
-
. -
. ,

.
.
,

, ,

1440

1441
. -- ,
LiAlH4 - .

LiAlH4 + 3(CH3)3COH

LiAlH[OC(CH3)]3 + 3H2

, . ,
, -78.

O
1)LiAl[OC(CH3)]3H

H3CO

; -780

Cl

2)H3O

OCH3

H3CO
OCH3
60%

1)LiAlH[OC(CH3)]3; ; -780

CH3(CH2)6 C

H
60%

1)LiAlH[OC(CH3)]3; ; -780
2)H3O

Cl
O
O2N

CH3(CH2)6 C

2)H3O

Cl
O

+ H2

C
Cl

CHO
42%

1) LiAlH[OC(CH3)]3; ; -780

O
O2N

2) H3O

H
81%

.
Pd/BaSO4, .

O
+ H2

CH2 C

Pd/BaSO4 (, )

O
+ HCl

CH2 C
H

Cl
70%

,
.

1441

1442

CH3
H 3C

+ H2

C
CH3

CH3

Pd/BaSO4; ;
; 1100

H 3C

O
+ HCl

Cl

CH3

80%

.
.
.

OMg
O
R1 C

R1

+ R2MgX

Cl

Cl

O
R1 C

+ MgXCl
R2

R2

(. 19)
.

R1 C

OH

OMgX

+ R2MgX

R1

R2

R2

R2

H 3O

R1

R2

R2

,
, .
RMgX
.

(III)
.

1442

1443

OMgBr

O
CH 3CH2C

+ CH 3(CH2)5MgBr
Cl

FeCl3
;

CH3(CH 2)5

-780

Cl

(CH2)2CH3
O

H 3O
H 2O

CH3(CH2)5 C

+ MgClBr
CH 2CH2CH3

95%

OMgCl

O
CH 3 C

FeCl3

+ CH3(CH2)3MgCl

CH3

; -780

Cl

Cl

(CH2)3CH3

O
CH 3 C

H 3O
H 2O

+ MgCl2
(CH2)3CH3
72%

-.

R2Cd + R1C
Cl
O
R2Hg + R1 C
Cl

RC

50-80%

AlBr3
CH2Cl2;

+ RCdCl

R1
RC

-200

80-100%
R1

,
.

-,

(. 19).
, ,
.

1443

1444

O
+ [((CH3)2CH)2Cu]Li

(CH3)3C C
Cl

;
-780

(CH3)3C C

94%
CHCH3
CH3

O
O

CH3(CH2)4 C

+ [(CH3)2Cu]Li

(CH2)4 C

;
-780

O
CH3(CH2)4 C
95% (CH2)4

Cl

C
O

H 3C
.

CH3
CH3

CH3

CH3CH2CH
C

+ [(CH3CH2)2Cu]Li

COCl

-780

CH3

CH3CH2CH
C

C
C

H
92%

CH2CH3

- ,
, .
, COOR CN-.

O
NC

(CH2)10 C

+ (CH3)2CuLi
Cl

-780

NC

(CH2)10COCH3

.
,

.

1444

1445

OLi

O
+ R1Li

RC
OLi

-300

OH

H3O

OLi

H 2O

R1

OH

R1

RCOR1 + H2O
O

1) CH3Li;

COCH3

2) H3O

OLi

91%

18.5.2. . - . (1927 .)

.

RCOCl + 2 CH2

00

O
+ N2 + CH3Cl

RC
CH

,
.
,
.

O
RC
CH

C
O
RCH

Ag2O
-
-N2
H2O

CH

RCH2COOH

. ,
.
. ,

13

, ,

1445

1446

O
C6H5 13C

CH

Ag2O
H 2O

C6H5CH2

13C
OH

, ,
. ,
. ( 26).

.
COOH
O

O
+ 2 CH2N2

C
Cl

CH2

C
CHN2

00

Ag2O
-
88%

18.6.
.

, .

O
R1C

+ R2COONa

O + NaCl

R1 C

Cl

OC

C6H5CH2COCl + C6H5CH2COONa

250

R2

(C6H5CH2CO)2O + NaCl
87%

(, .).

O
RC

O
+

OH

RC
Cl

C 5H 5N

O

CH3(CH2)5COOH + CH3(CH2)5C

C 5H 5N
Cl

1446

O
O

RC
OC

+ C5H5NHCl

(CH3(CH2)5CO)2O + C5H 5NHCl

97%

1447

.

t0

RCOOH + (CH3CO)2

t0

C6H5COOH + (CH3CO)2

(RCO)2O + 2 CH3COOH

(C6H5CO)2O + 2 CH3COOH
74%

.
.

O
CF3COOH

P2O5
t0

CF3C
OC
80%

CF3SO3H

P2O5
t0

+ HPO3

CF3

(CF3SO3)2O + HPO3
72%

,
N,N-.

RCOOH + C6H11N

NC6H11

C6H11NH C

NC6H11

OC

O
RCOOH

(RCO)2O + C6H11NHCONHC6H11
N,N`-

.
, , .

1447

1448

O
CH2C

CH2COOH

3000

CH2COOH

+ H 2O

CH2C
95%
2300

COOH

+ H 2O

COOH

C
O

100%

.
- - -
.

HCOONa + CH3COCl

HC

250

+ NaCl

CH3

64%

N(CH2CH 3)3

RCOOH + Cl

CH 2Cl2

OCH2CH3

; 0-50

RCOOH + CF3C

RC

+ NH(CH2CH 3)3Cl

OC

OCH2CH3

O
O

CF3COOH + CF3C

O
C

OC
CF3

.
-, -
,
.

1448

1449

O
COOH + ClC

RCH

N(CH 2CH 3)3

OCH 2CH 3

RCH

; 00

NHCBz

OC
OCH2CH3

NHCBz
O
C

RCH

O
+ NH 2CH

OC
OCH2CH3

NHCBz

COOCH3

00

R1

O
RCH

NHCHCOOCH 3 + CO2 + CH3CH2OH

R1

NHCBz

.
.
, , .

NH2 + (CH3CO)2O

CH3CH2O

NaOH
H2O

NHCOCH3

CH3CH2O

( )

O
CH2COOCH3

CH2C
O
CH2C

95%

+ CH3OH

CH2COOH

18.7.
- (3)2
- 2==.
2==2 (. 7)
==.
7000.

O
7000

CH3C

CH4 + CH2

CH3

1449

90%

1450
: RCH=C=O R2C=C=O

2-

O
RCH2C

Cl

R
R

N(CH2CH3)3; t0
C6H6
O

C
Br

RCH2

Zn
C6H6

O + ZnBr2

Br

O + HN(CH2CH3)3Cl

, .
, , , .

O
CH2

CH2

CH2

CH2

O + HOH

O + ROH

CH3C

OH

CH3COOR
O

O + R2NH

O + RSH

CH3C

C 6H 6

NR 2

CH3C
SR

O
CH2

O + CH3C

(CH3CO)2O
OH

,
, .

1450

1451

O
O + HC

CH2

CH3C

OH

CH3C

+ RNH2

C6H6

+ H3COOH

RNH
H

, -200
.

CH2

CH2

CH2

CH2

CH2

CH 2

+ H 3CH2OH
O

N(CH 2CH3)3
H3CH 2OH; 0-200

O
CH 3C

CH 2C

OH2CH 3

18.8.
.
,
.
.
,
.
.

18.8.1.

18.8.1..

.

1451

1452

R1COOH + R2OH

R1C

+ H 2O
OR2

,
.
. (1895 .).
, ,
n-, 70-80.
.
, .
,
-.
, n-
.
- 3 4 .
,
,
.

- , 4-, N,N-,
.

20. .
O

CH 3(CH2)7COOH + CH3OH

3A; H2SO4
CH3OH

C 6H5CHCOOH + CH3CH 2OH

HCl
CH 3CH2OH

CH3(CH 2)7COOCH3

96%

C6H 5CH 2COOCH 2CH 3

85%

80
CH3CH2OOC(CH2)4COOCH2CH 3 95%
HOOC(CH2)4COOH + 2CH 3CH 2OH

O
C6N 5N(CH3)2
+ (CH 3)3COH
72%
CH 2C
CH 2COOC(CH3)3

Cl
CN
CN
CH 3(CH2)5COOH + CH 3OH

CH3OH BF3

1452

CH 3(CH2)5COOCH 3

93%

1453

. -
- - - - .
H3C

CH3
H3C

CH3 H3C

COOH + HO

CH3

(CF3CO)2O

H3C

CH3

CH 2Cl2; 20

H3C

COO

CH3

CH3 H3C

H3C

94%
O

CH3

COOH
OH

(COCl)2; N(CH 2CH 3)3

CH3

86%

O
CH3CHCH 2CH 2COOH

H 2SO4

H 2O

95%
CH3

OH

18.8.1..
,
.
.

R1COOR2 + R3OH

H2SO4

R1COOR3 + R2OH

,
.
,
.

CH2OOC
CHOOC
CH2OOC

CH2

C11H23
C11H23 + CH3OH

H2SO4

C11H23

RCOOCH3 + (CH3)3COH

C11H23COOCH3 + CH
CH2

(CH3)3COK
RCOOC(CH3)3 + CH3OH

1453

OH
OH
OH

1454


.

CH3

CH3
O

11O
COOH + HC(OCH2CH 3)3

H3C

CH3

H3C

COOCH2CH3 +
63%

CH3

+ HCOOCH 2CH3
C6H5COOH + (CH3)2N
+ HCON(CH 3 )2

CH(OCH2CH3)2
O
8O

C 6H5COOCH2CH3 + CH3CH 2OH +

90%

,
.

18.8.1.. -
SN2 -
-
.
-
(, ), -

. (. .9)

,
,
, .
18--6-.

1454

1455

CH3CH2COONa + . CH3(CH2)3Cl

. C4H9N (CH2CH3)3Cl ; NaI; 200

CH3CH2COO(CH2)3CH3
(CH3)3CCOOK + BrCH2COC6H5

87%

18--6

(CH3)3CCOOCH2COC6H5

BrCH2(CH2)9COOK

1000

89%
18.8.1..

.
,
, .

RC

N + 2 HCl

RC

NH2Cl

CH3CH2OH

Cl
H2O; 200

NH2Cl

OCH2CH3

RCOOCH2CH3

O
CH3C

RC

CHCN

O
1) HCl;
2) CH3CH2OH

CH3C

C6H5

CH
C 6H 5

NH2Cl
C

H2O

OCH2CH3

O
CH3C

CH

COOCH2CH3

50-60%

C 6H 5

18.8.1..
, ,
. 1894 .

1455

95%

1456

RCOOH + CH2

-100-00

RCOOCH3 + N2

CH3 CH3

CH3 CH3
CH2N2
; 00

HOOC

CH

+ N2
H

CH3OOC
H

C(CH3)2

CH

87%

CH2N2
; 00

+ N2

COOCH3

COOH

91%

H3

C(CH3)2

COOH + CH2N2

; 00

C
C
80%

H3

COOCH3 + N2

18.8.1..

, . -
,
.

C6H5

Br
C

Ni(CO)4; CH3ONa

CH3OH; 250

C6H5

COOCH3
C

H
78%

,
- .

RI

Ni(CO)4; (CH3)3COK
(CH3)3COH; 500

1456

RCOOC(CH3)3

1457
- , -
Pd(II) .

CH2

CHBr + CO + ROH

R3N; Pd[P(C6H5)3]2Cl2
1000

CH2

CHCOOR

18.8.2.
, .

- .
-
( 17). -

(CH3)2CH

CH(COOCH2CH3)2

. HCl
1150

(CH3)2CHCH2COOH + CH3CH2OH
75%

, , -
NaOH KOH.
, .

CH3(CH2)8CH

COOCH3 + KOH

- (9 : 1); 800

CH3
CH3(CH2)8CH

COOK + CH3OH

70-80%

CH3
-NO2C6H4COOCH2CH3

[(CH3)2CH]3CCOOCH3

NaOH
-NO2C6H4COONa
H2O; 1000
KOH
-H2O; 1000

90-96%

[(CH3)2CH]3CCOOK
73%

,
- 18--6-:

1457

1458

CH3
H 3C

CH3

COOC(CH3)3 + KOH

18- -6
-; 1000

H3C

COOK

CH3

CH3
80%

, ,
.
, , .
, ,
.

18.8.2..
,
:

+ H2O
O

+ R1OH

R1

OH

, -
(. 3).
.
:
(1) : ( ) ( );
(2) , , - -
: - ( ) - (
L):

CO

OR`

HO

COO
H

R`
OH

-
(L)

-
()
(3) (1 2).

,
18.1.

1458

1459

18.1.


AAC2
OH

OH
R

H2O

OR1

OR1

OH2
BAC2

OHR1

-R1OH

OH

O
R

OH

OH

OH

OR1

OR1

-R1O

RCOOH

RCOO

OH
.
2. ( )
2.

AAC1 RCO

OHR1

BAC1 RCO

-R1O
OR1

H2O

RCO

-R1OH

OH

RCO

OH2

RCO
RCOOH

RCOOH

RCOO

1 (, .
H2SO4), .
1 .

AAL2

C
OH

BAL2

COO

RCOOH + R1

R1

OH2

H2O
RCO2 + R1OH

R1
HO

L2

-. AL2
.

1459

OH

1460

OH
AAL1 R1

BAL1 R1COO

R1COOH + R ; R + H2O

R1COO + R

H 2O

R1COOH + ROH

AL1 -
. L1,
L1
2.
18.1, , , ,
(.2) ,
.
(),
.
1 COOR COOH
. ,
, C=O, ..
:

O
R

O
R

OH

+ H+.

C
O

1. 1 - ( 1 )
,
.
.

18.8.2.. 2 2

2 2. ,
.
- . ,
H218O
(. ), , 18
, - , (.. ).

1460

OH2

1461

O
C

C2H5

NaOH

18

OC2H5

H 2O

C2H5COO Na

18

+ C2H5 OH

.
. , ,
- .
2 2
, ( 18.1).

18

(. , 1951), ,

H218O

. , , , ,
:

O
+

Ph C

18

OH

Ph

OR

OR

18

OH
PhCOO + ROH
OH

OR
Ph C

OH

Ph

18 O

OR

18

. , ,
,
.
2
,
. ,
( = 2.5). , 2 -
; , , ,
,

1461

1462
. ,
( 1,2), ( -0,2).

18.8.2.. L -
L -
,
- (AL), (AL).
.-
,
.
. -
, . ,
- 20%- 2SO4 , , ,

.


2, ,
AL1:

CH3
OH
CH3
(CH3)CH(CH2)3

C*

O
O

(CH3)CH(CH2)3

C*

C 2H 5
()

CH3
H

C 2H 5

ROH
()

- 0.01 HCl H218O,

-.
. , AL1 A2:

AAl1
O

18

CH3COOH + t-Bu OH

18

+ H2 O

CH3C
O

18

t-Bu
AAC2

CH3CO OH + t-BuOH

()

1462

OH

1463

O
R

pH7

Ph

C
O

RCOO + Ph3C

Ph
Ph

()
, -. AL1 ,

. A2 ,
. RCOOCH2C6H5
A2.
AL1 ( )
, AL1. -.

CF3COOt-Bu

(CH3)3C + CF3COO

H2 O

(CH3)3COH

AL1 A2.
Al . AL2
, A2 .
( ), ,
( ) .
, . ,
2,4,6--
( ) AL2, 2,4,6 A2 - .

C(CH 3)3

C(CH 3)3
O
(CH 3)3C

BAl2

C
O

CH3

COO

(CH 3)3C

+ CH3

C(CH 3)3

C(CH3)3
OH

AL2 -,
. .
18, :

1463

OH

1464

18

H2 O

H 3C
O

H 3C

COOH

18

HO
O

,
- ( 1).

H
H3C

OH

18
H2 O

OH

18

CO OH

H
CH3

18.8.2.. 1

RCOOR

RCO

+ RO

) (1) , ,

, ,
, , .

100%-

2,4,6-

, - :

ArCOOH + 2 H2SO4

ArCO + H3O + 2 HSO4

ArCO

ArCOOCH3 + 3 H2SO4

+ H3O + CH3HSO4 + 2 HSO4

:
H2SO4, .
: H2SO4
.

18

-. (S = +17 .-1-1)
.

18.8.3..
, 2
, ,
. ,

1464

1465
. -
.
: - (. .3).
:

R
R

O
H

BH + HO

OR1

RCOOH + OR1

C
OR1

, RCONu,
:

Nu

CO

OR1

CO

Nu + R1O

+ H2O
RCOOH + NuH

.
, ,
, ,
.
.

( ), .
(.3).
, ( =
0,47) pKa , ,
, -, HPO42-. , ,
, ,
, .. .
(pKa
(H3O+) = -1,75); , - ,
:

1465

1466

H 2O

O
H

H3O + HO

OR1

OR1

,
pKa . ,
(pKa (H2PO4-) = 7,2) (pKa BH4) = 7,0)
, n- 5000 HPO42-.

O
C

CHCl 2

OC2H5

H
N

CHCl 2

OC 2H 5

OH

NH

N
H

N
H

CHCl2COOH + OC2H5
O

O
CH 3

C
O

NO2

N
H

CH 3

N
NH

(B)
O

H 2O

NO2

CH3COOH + BH
- (.9). , -
HOO- 400 , OH-,
, pKa (H2O) = 15,7, pKa (H2O2) - 11,6.
RCO-B.
n-.
2,4--,

18

-,

,
, ,
18 :

1466

1467

18

O
18

CH3C O2 + C 6H5

CH3

NO2
NO2

18

C6H5 + ArO

OH2

18

18

CH3C OOH + C6H5CO OH

, , :

Ac2O + ArO

ArO + AcOAr

C6H5NH2
C6H5NHAc + AcOH

18.8.3..
( ) 3 8
, -.
3,4, ,
. -

1467

1468

H
CO2

COOH
OH

CH3

COOH
+
CH3

OH

O
+ CH3COOH

COOCOCH3

COO

COOH
+ CH3COOH

H 2O
O

COCH3

OH

(+H)

,
.
,
:

CO

COO
C 6H 5O +

H2O

O
CO

COOC6H5

COOH

COOH

;
,
.
. 3.

18.8.4.

, (.
).

O
+ R2OH

RC

R2ONa; R2OH

O
+ R1OH

RC
OR2

OR1

1468

1469
,
,
(18.8.1..), R1OH R2OH
, , .

O
CH3ONa
CH3OH

+ CH3OH

RC
O

NO2

RC

ONa

O2N

+
OCH3

18.8.5.
,
.
. ,
, ,
.

O
COOCH 2CH 3 + NH3

CH 3CH

-; 250

+ CH3CH 2OH

CH3CH
NH 2

OH

OH
85%

CH 2COOCH2CH 3 + NH3

-;

250

+ CH 3CH2OH

O
CH 2C

86-88%

+
NH2

-
.

+ NH 3

RC
OR1

O
R

OR1

RC

O
OR1
H

RC

+ R1OH
NH 2

NH 3

NH 3

- ,
n- n-.

1469

1470

18.8.6.

( 11).

H5C2OOC

(CH2)4

COOC2H5

1) LiAlH4;
2) H3O

HO(CH2)6OH + CH3CH2OH
90%

.
.
.

CH3(CH2)14COOCH2CH3 + LiBH4

650

CH3(CH2)14CH2OH + CH3CH2OH
95%

NaBH4 + LiCl

LiBH4 + NaCl

. ( 11),
.

- .

C11H23COOCH2CH3 + Na + CH3CH2OH

CH3CH2OH; 780

C11H23CH2OH + CH3CH2OH
74%
-
.

O 1) LiAlH4;
2) H3O

HOCH2CH2CH2CH2OH
83%

,
, .

1470

1471
(-).
. ,
, (60 - (-780) , -
.

CH3(CH2)10COOCH3 + -(4H9)2AlH

1) ; -600
2) H3O; H3OH

CH3(CH2)10CHO 88%
(CH3)2CHCOOCH2CH3

1) -; ; -780

79%

(CH3)2CHCHO

2) H3O; H3OH

.

.

()

-(2-

) .
.

(CH3)3C

COOCH3

LiAlH2(OCH2CH2OCH3)2
; 00-(-200)

(CH3)3C

CHO

81%

18.8.7.


( 19).

1471

1472

H3CH2COOCH2CH3 + 2 CH3CH2CH2MgBr

H3CH2C(CH2H2CH 3)2
OH

O
C 6H 5C
H 3O
H 2O

OCH2CH3 + 2 C6H5MgBr
(C6H5)3COH

2) H3O

(C6H5)3C

OMgBr

96%

1) 2CH3MgBr

70%

CH2CH2CH2CH2OH

(CH3)3C
OH

72%

,
. ,
, ,
. .-
.

O
(CH 3)3CC

OCH2CH 3 + (CH3)3CLi

O
;

250

(CH3)3CC

C(CH3)3 + CH 3CH2OLi

80%
Mg Li-
.

1472

1473

19

19.1. ................................................................... 1476

19.1.1. RLI . .............................................................................................. 1476
19.1.2. ........................................ 1476
19.1.3. ............................................. 1478
19.1.3.. ............... 1478
19.1.3.. 1479
19.1.3.. - ....................... 1480
19.1.3.. .................................. 1484
19.1.4. ................................................................. 1485
19.1.4.. (.19.1).............................................................................................. 1485
19.1.4.. (.19.1)..................................................... 1488
19.1.5. .................................................................................................. 1491
19.1.5.. ............................................ 1492
19.1.5.. .............................................................................. 1493

19.2. ................................................................ 1496

19.2.1. ...................................................................................... 1496
19.2.2. .......................................... 1498
19.2.3. ................................. 1499
19.2.3.. - ...................................... 1499
19.2.3.6. - - ................ 1501
19.2.3.. - ................................................. 1505
19.2.3.. .................................................................. 1506
19.2.3.. ................................................................................. 1508
19.2.3.. ................................................... 1509

19.3. ........................................................ 1510

19.3.1. .......................................................... 1510
19.3.2. ................................................... 1511
19.3.2.. ........................................................................................ 1512
19.3.2.. .............................................................................................. 1513
19.3.3. ........................................................ 1515

19.4. ..................................................................... 1519

19.4.1. ............................................................. 1520
19.4.2. ................................................................. 1524
19.4.2.. ........................................................................................ 1524
19.4.2.6. ................................................. 1525
19.4.2.. .......................................................................................... 1526
19.4.2.. ................................................................................. 1527

19.5. ........................................................................... 1527

19.5.1. ................................................................................... 1528
19.5.2. ............................................................................... 1531
19.5.. ................................................................................. 1538

19.6.
............................................................................... 1543

-

1473

1474
, .
. ,
-
.
.
: -, ..
;
27.
, , -,
-, .. .

.
18 16 .
- ( m ,
, m = Li, MgCl, HgCl2, Sn(CH3)3 ..).
.
R - X + 2m R-m + m-X

(19.1)

(X = Cl, Br, I)
.
R - X + R-m R-m + R-X

(19.2)

(X = Cl, Br, I, OR, OAc, SAr)

- .
R - H + R-m R-m + R-H

(19.3)

- .
R - X + m R-m + 1/2 H2

(19.4)

.
R - m + m R-m + m

(19.5)

.
R - m + m-X R-m + m-X

(19.6)

, , R2l,

( 19.5.2).

. ,
(),
, .
, ( ), ( )
. ( , , -

);

1474

"

1475
", -,
.. " " , -
:

Li

MgX

AlR2

.19.1.
19.1

- R-m (m = Li, g ,
lR3, ZnX ..) ( Z - )
1. ( mZ)
1

R-m + H-Z R-H

()

R-m + Z-B(OR)2 R- B(OR)2

()

R-m + Z-R R-R

()

R-m + >C=C-C-Z R-C-C=C<

( )

R-m + -CC-C-Z R-C=C=C<

(
))

R-m +

R-m + Z-C=C< R-C=C<

( )

R-m + Ar-Z R-Ar

( )

R-m + Z-C=O R-C=O

( )

10

R-m + Z-CN R- CN

( )

11

R-m + Z-Rn R- Rn

( )

( )

R-C-C-OH

(=Si, N, P, Hg, Sn, Pb ..)

12

R-m + Z-NO2 R- NO2

13
R-m + O 2

H 3O

ROOH

( )
[H]

()
R-O

14

R-m + Z2 R-Z

()

15

R-m + S8 R-S-

( )

R-m + Z-SR R-S-R

2.
16

R-m + >C=C< R-C-C-H

( )

17

R-m + -CC- R-C=C-H

( )

18

R-m + >C=N- R-C-NH-

( )

19

R-m + >CN R-C=NH

( )

20

R-m + >C=O R-C-OH

( ,
)

21

R-m + CO2 RCOOH

()

22

R-m + CO R2CO

()

1475

1476
23

R-m + CS2 R-CSSH

( )
-

, ..
.

19.1.
19.1.1. RLi
RLi

(R = ), RMgX ( -

),
R-. a RLi R-.
? ,
RLi R- - , RLi ( RLi )6, (
RLi

)4

..,

.
, -Li,
. (~ 5,7 ),
a ,

-Li

. ,

, ,
( ).
Li4 -Li, ..
C4- ... 4Li+ ( !)
-, , - ..
R- Li+ .
- - . ,
, CHLi3 (I), (II)
, a 1,1- - , (III).

H
Li C
Li
I

H
Li

Li

Li
II

Li
Li

C C
Li

H
H
III

. 2 (
2.5.1.).

19.1.2.
RLi ,
. ,

1476

1477
. ,
,
.
,
. , -C4H9Li -, - .
-49Li , a
.

.
(RLi2), , , C6H5Li ,
, 5+ ( 4),
, .. (1V).

Li

Li
R
Li

Li
Li

R
IV

, CH3Li, C2H5Li, -C4H9Li, C4H9Li, CH3Li -C4H9Li

25Li ,

(V), .. .
VII,
, . - .
7Li

13

.
-Li (VI)
.

M
R

R M

M
R

R
VI

R
M

M
R

VII

(VIII).

R M
R
M

R
M

R
R

R
R

M=Li

VIII

CH3

CH3
M
CH3

IX

1477

CH3
M

1478
, (IX),
sp3- . ,
, (V).
,
.
. ()

:
+

O:

Li

N,N,N,N-

(),

1,4-

[2.2.2] () ..

CH3
CH3

N CH2CH2 N

CH3

CH3

R1R2R3CLi
, .. . ,
. .5 ( 5.5.3).

19.1.3.
ao
( 19.1, 19.2 19.3),
.

19.1.3..

RX + 2Li

R-Li + LiX

(19.7)

, (

19.2), ,

, ,
RX, .. .
.

1478

1479
, ..
:

2RI + 2Li

R-R + 2Li

, .
19.7 ,
.
.
- - 19.7
, - ,
, .

CH2Li + LiOR

CH2OR + 2Li

OR

Li

+ 2Li

+ LiOR

CH3
(R=Alk, C6H5, -C

CH3)

, , , :

RO-CH2-SC6H5 + 2Li

RO-CH2-Li + C6H5SL

19.1.3..


:

RX + R'Li

RLi + R'X

(19.8

(X=Cl, Br, I)

; ,
.
RLi

, .
.

C6H5Br + -C4H9Li

50 oC

1479

-C4H9Br + C6H5Li (95%)

1480

NO2

-100 oC

+ C6H5Li

Br

NO2
C6H5Br +

(97%)

Li

C6Cl6 + -C4H9Li
(C6H5)2C=CHBr + -C4H9Li

-75 oC

-76 oC

-C4H9Cl + C6Cl5Li

(82%)

-C4H9Br + (C6H5)5C=CHLi (100%)

COOLi

COOH
-75 oC

+ 2-C4H9Li

(62%)

-C4H9I +

Li

I
CCl4 + -C4H9Li

-100 oC

-C4H9Br + CCl3Li (76%)

, - 78
-100. ,
, , ,
, :

(CH3)3SiO

Br

+ AlkLi

(CH3)3SiO

Li

CH2CH2Br
+ AlkLi

CH2CH2Br

Br

Li

+ AlkBr

+ AlkBr

O
+ AlkBr

+ AlkLi
Br

Li

(Alk = -C4H9, -C4H9; -70- -100 oC; )

, .
.
( 19.8) .

19.1.3.. -
- .

1480

1481

R-H + R'-Li

R'-H + R-Li

(19.9)

, , RH , RH, ..
pKa(RH) < pKa(R'H). H- (.15.6)
RLi 19.9
; -,
. ()
R RH; , 19.9 .
( ),
( ) (,
- ) (, ),

. , ,
RLi:

CH3

CH3
N

-4H9Li

CH3

-C4H9Li

CH2
CH2

()

,
-C4H9Li

CH3

:O=R[N(CH3)2]3
()

:O=R[N(CH3)2]3

(> 90%), , ( .5.16):

(C6H5)3CH + R'Li

(C6H5)3CLi + R'H

(pKa=30,6)

+ C6H5Li

Li + 6H6

(pKa=18)

CH3
+ -4H9

CH2Li
+ C4H10

(pKa~42)

C6H6 + -4H9
(pKa>42)

Li + C4H10

R .

1481

1482
1) (-I)- ( -NR2, -OR , -HaI)
-:

CH3 O:

OCH3

Li
-BuLi

(65%)

(CH3)2N

OCH3

-BuLi

(CH3)2N

OCH3
Li

-
( 5.5.3.). -
(.. ) ,
RLi. ,

-:

(CH2)nX

(CH2)nX
Li

+ R'Li

+ R'H

-
:

CH2N(CH3)2

CH2N(CH3)2

H Li

+ R'Li
CH3

CH2 N

- R'H

CH3
CH2N(CH3)2
Li

Li

(92%);
R = -C4H9

2)
-
.

1482

1483

-BuLi

( 95%)

Li

2R-

-BuLi
Et3N

(C6H5)2P-CH3

Li

-BuLi

(C6H5)2P-CH2Li (84%)

-BuLi

CHCl3

X = O, S

(100%)

CCl3Li

; -100 oC

(> 90%)

RCH2CH2X

R'Li

X
RCH2CH

(X=OR")

R CH CH + LiX

Li

R CH CH2
3) , (-)- (-N, -R ..), - , -
(.5.16).

ArSO2CH2R
CH3CN

-BuLi

-BuLi

R
ArSO2CH

Li

(65-78%)

LiCH2CN ( )

,
RLi .
, ,
, , .. ,
-CN -COR.
(
, ).
, (
.5.16). (X) 2,2,6,6--
(XI) , 3,3,6,9,9--2,10- 4.4.0 1 (II).

1483

1484

CH3
CH3
CH3

CH

CH3

2NLi

CH3

CH3

CH3
N
Li

CH3

CH3

CH3

XI

CH3

Li

XII

Bu
C NLi

C N

C N -BuLi

-BuLi

(-Pr)2NH;
,

CH3

CH3

CH2Li

O
NR

NR

Li XII

O
Li

( = )

-II
(. ).

19.11:

H2Br2

(-C6H11)2NLi

CHBr2Li ( )

19.1.3..

.
, , , , .
,
. .

(C6H5CH2)2Hg + 2Li

2C6H5CH2Li + Hg

1484

1485

Li

Hg

Li

+ 2nLi

+ nHg

R'

OCH3

Li

+ 2RLi
R

Sn

OCH3 Li

R'

+ R4Sn

1,5--3--3--1,5

19.1.4.
.19.1
.

19.1.4.. (.19.1).
. ,
,
( 19.1.3.). ,
, :

CH3Li + D2O

CH3D + LiOD

R-Li + FB(OR')

R-B(OR')

-LiF

H 2O 2

ROH

. R-R
, - (. 19.1.5).
, Z , , . SN2
( -):

SN2:

Li

Li

1485

R C

1486

SN-.
.
(=0 ) (n =1),
( =2), :

CH2
Li + O

RCH2(CH2)nCH2OLi

(CH2)n
CH2

n=0,1 ( 2,3)

. -
. ,
, , Ni Pd ( u).
. ,
, SN2-
:

-BuLi +

Br

R'

R"

Li

R'

R"

-BuBr +

SN2

+ -BuBr

Li

R'

R"
C4H9

R
R'

R"

, ,
-, -
.
:

Li
X
+ RLi

X
RLi
-LiX

-RH

R
Li

RH

+ RLi

().
RLi
( ,
R2RCOH). , .

1486

1487
, RLi
-

RCOCl,

a RCOO Li . o ,
:

R'

R'

O
O Li

+ R

Li

R'

H3O

2Li

C O
R

XIII

O
CH3

CN + RLi

CH3

S O Li

+ R-CN

.
, , :

(CH3)3SiCl + R-Li

(CH3)3Si-R + LiCl

100%.

, R' -
;
, , ,
.

(CH3)3Si-Cl

(CH3)3SiCl

(CH3)3Si Cl

R-CH2CH2 Li

R-CH2CH2 Li

R-CH2-CH2-Li

SET- (single
electron transfer). , ,
, ,
SN2-.

:

R O N

+ Ar

Ar

Li

+ RO Li

1487

1488
. , ,
, ,
( ).
,

.

R-Li + O2

R-Li O2

H3O

R-O-O Li

ROOH

[H]

ROH
:

R-Li + MoO5.Py

[H]

R-O-O-Mo-

ROH

(Py = , C5H5N)

, (-)-,
1,2-, 1,4-, 1,4- .

Li

NO2

I2

NO2 NO2
+

Li

CR

Cu2

C=O C=O

R
Li

CR

Cu

C=NR C=NR

NR

19.1.4.. (.19.1)
.
. ,
-uLi .
:

1488

1489

R
RLi

__

RLi

R
[O]

()

.
.
, .. ,
.
"" .

CH3

CH3

CH3

R-Li + nCH2=C-CH=CH2

R-(CH2-C=CH2)n-CH2-C=CH-CH2 Li

CH3
H2O

R-(CH2C=CH-CH2)n-H + LiOH

=N

N. -

.
1,2- ( 1,4-).
2,5- .

+ RLi
N

H
N
CH3I

CH3

R
1. CO2
2. H2O

Br2

Br
N

HOOC
N

Li

R
1. R'2CO
2. H2O

ClNH2

R'2C
OH
N

1489

H2N
N

1490

R'Li

C N

H3O

R C NLi

R'

R'

C O

R'Li

R
R' C NLi2
R'

R
R' C NH2
R'

H3O

=O C=S.
, .
, , - .

RLi + H2C=O

H3O+

RCH2OLi

RLi + R'HC=O

RCH2OH
R'

H3O+

R'CHOLi

CH-OH
R

R
R'
RLi + C=O
R"

R
R' COLi
R"

H3O+

R' C-OH
R"

, , SET.
(-)
. ( S-.)

CH3CCH3 + RLi

RH + CH3 C

O
ArCH2

O Li

Li

C2H5CH CH2

Li

O
Ar2C=O

CH2

C2H5CH=CH2

.
, ..
,

(-C4H9)2CO + -C18H37Cl + Li

1.
2. H3O

1490

(-C4H9)2-C-C18H37-
OH

(74%)

1491
,-
1,2- ,
1,4-,
( 19.2) - 1,4. ,
3gr -3- 25 oC 1,2- (IV)
1,4- (V). IV, V.
CH3Li

CH3CH=CH2-C-CH3
O

86%
14%

CH3MgBr
(CH3)2CuLi

CH3CH=CH2-C(CH3)2OH
XIV

(19.10)

(CH3)2CHCH2-CO-CH3
XV

2
(.19.1). 2
RLi, III, .
(, , )
, ,
:

(C6H5)2C=S + -C4H9Li

(C6H5)2C-SC4H9
Li

"" .

19.1.5.
,
, .
RLi "a-",
, , :

MXn + RLi

-LiX

RMXn-1

(n-1)RLi
-(n-1)LiX

RnM RLi

[Rn+1M] Li

a-

(M=B, Al, n=2; M=Cu, n=1)

a-K , .
[R2Cu]Li ,
(I) .

2RLi + Cu2I2

0- -70 oC

[R2Cu] Li + L

. ,
RCu. :

RCu + RLi

[R2Cu] Li
1491

1492
, ,
0 o. in situ.
,
. , .
; ,
R4Cu2Li2, , R

, ,

(CH3)5Cu3Li2. :

R
R

Li
Cu

Cu

R
R

Li

19.1.5.. .
:
- ( a-) ( 19.10)
1,2- , 1,4-, ..
(1),
3.

,-

,
. , -
: O, 1, 2 C3. ,
( ) C3 ( 3* .2.20).
.
3

C3

C2 C1

3 , (.
2.3.6).
() ( 5.2.3). , 1,4 . -
, ,
1, ( + ) , C3, .
- (
5.2.3).

1492

1493
,
(a 5.2.2).
Li+, - Cu+ (
. 5.3).
, , ,
. - , ,
.
. , ..
( ) .
, ,
(, -

- ),

, .
.

19.1.5..
,
. ,
, "-" ( ).

. .

[(CH3)2Cu]Li + CH3(CH2)8CH2I

CH3(CH2)8CH2CH3 + [CH3Cu] + LiI

[(CH3)2Cu]Li + 6H5I

C6H5CH3 + [CH3Cu] + LiI

[(C4H9)2Cu]Li +

(90%)
(91%)

-C7H15

-C7H15

-1--1

[(CH3)2Cu]Li +

C4H9-+ [C4H9Cu] + LiI

-5-

[(CH3CH2CH)2Cu]Li + CH3(CH2)3Br
H3

CH3CH2CH(CH2)4CH3
CH3

1-

3- (64%)

Br
H

CH3

C6H5

--

Br
Br

+ 2[(CH3)2Cu]Li

7,7-

H
C6H5

--

-15

H3
CH3

(65%)

7,7-

1493

(81%)

1494
1855 ,

2RX + 2Na

RR + 2NaX

2C20H41Br + 2Na

C40H82 + 2NaBr

1-

(31%)

RX + 2Na

R Na

R Na

+ RX

+ NaX

RR + NaX

. , (
) -
, , .
.

. , , ,
. 9-Z-,
- Z-1-- :

-C8H17

(CH2)7CH2Br
+ [(-C5H11)2Cu]Li
H

C13H27-

- 9-Z-

Z-1--9-

-C8H17

.
-,
,

,-

(),

1,1-

. .
, .

H3(CH2)4C-Cl + [(-C4H9)2Cu]Li

-78

-5

O + [(CH3)2Cu]Li

(CH3(CH2)4CO(CH2)3CH3

CH3

-2--1

1494

(79%)

(98%)

3-

1495

OH
:

O + RLi ( RMgX)
R
O

C2H5

+ [(CH3)2Cu]Li

CH3CH2-CHCH2CH3
OH

CH3

-3 (98%)

CuLi
2

CH3

O2,
-78

CH3

,-1,3- (78%)

CH3

H
COCH3

+ [(CH3)2Cu]Li

4--2 (85%)

I(CH2)10C

-78

+ [(CH3)2Cu]Li

Cl

CH3CHCH2C-Cl + (CH3-C=CH)2CuLi
O

CH3

3-

(CH3)2CHCH2COCH3

-5

I(CH2)10COCH3 (91%)
12--2

CH3CH-CH2-C-CH=C-CH3
CH3

CH3

2,6--2--4- (70%)

. ,
. ,
, :

NC(CH2)3C-Cl + [(CH3)2Cu]Li

NC(CH2)3COCH3
(85%)

O
CH3(CH2)4O(CH2)4C-Cl + [(CH3)2Cu]Li

CH3(CH2)4CO(CH2)4COCH3
2,7-

(95%)

- .

.

H3O

I + [(-C4H9)2Cu]Li

H3O

C4H9-
(70%)

,- ,
, SET-, .

1495

1496

Li

[R4Cu2Li2] + CH3CH-CH=CH-CCH3

Cu + CH3CH=CH-C-CH3

Cu
R

Li

CH3

Cu

[R3Cu2Li2] + RCHCH=CHCCH3
O

1/2 R4Cu2Li2 + [RCu]

Li

CH3

Cu
Li

CHCH=CCH3
O

(R 2, RH, R-H, Cu)

,
, . ,
, [R(RCC)Cu]Li,
[R(-BuO)Cu]Li [R(PhS)Cu]Li.
(I) :

C6H5SCu + RLi

[R(C6H5S)Cu]Li

19.2.

. ,
,

R2Mg RMgX.
.
. 1900 ,
. ,
. ,
, ,
. , .. RMgX
, ,
, , ..

19.2.1.
RMgX ,
(S). (VI).

1496

1497
, (VII),
.

S
Mg

R
X
X

Mg

Mg

R
XVI

S
XVII

. RMgX
, , , R2Mg
. .
. ,
(), (. VI
VII).

2RMg

+ 2X

X
RMg

MgR

R2Mg + MgX2

2RMgX

(19.11

X
X
RMg

R2Mg

+ RMgX2

Mg
X

, , R X,
, .
(, )
, .
, o
, .. VI. .
,
.
,
, ,
"RMgX".

1497

1498

19.2.2.
-
a ( 19.1).

R-X + Mg

RMgX

(X=Cl, Br, I, F)
.
, (, ), ,
RMgX,
-(-) 3(22))n CH3.
.
, 1,2-
. :

Mg + I2

MgI2

Mg + BrCH2CH2Br

CH2=CH2 + MgBr2

c .
RX RI > RBr > RCl,
, - .
, ,
in situ MgCl2 .

MgCl2 + 2K

2KCl + Mg ()

,
:
2 CH2=CH-CH2Br + Mg CH2=CH-CH2-CH2-CH=CHC2
, (
, )
.
-, ,
.
( "s"):

RX + MgS

{RX

{R MgSX}

MgS+}

{R MgSX
RMgX + Mg

, ,
.

1498

1499

R2Hg + Mg

R2Mg + Hg

, ,
( 19.11) ,
MgCl2, , . MgCl2 .
:

2RMgX

R2Mg + MgX2

R2Hg + MgX O

, :

CH3CH2CH2CH2CH2Cl + Mg

(C5H11)2Mg + MgCl2

1-

:
R'OH
R'R"NH

R2Mg

R'SH

RH + RMgOR'

RH + RMgNR'R"

RH + RMgSR'

,
:

CH2I2

Mg

CH2

Mg

MgI

CH2(MgI)2 + R2C=O

CH2(MgI)2

R2C=CH2 + MgO + MgI2

19.2.3.

19.2.3.. -

(RCCR) , (RCCH)
(. 6.3). , ,
, CF2=CF2.
,

1499

1500

MgX
MgX
CH3

CH3
1-(5-)
+

Mg

H3O

(88%)

CH3

Cl

CH3

CH3

1,2-

6--1

(RO, R2N), :

C6H5CH2MgX + CH2=CH-CH2OH

CH2=CH-CH2-OMgX

-C6H5CH3

CH2C6H5

C6H5CH2MgX

O MgX

XMg

C6H5CH2 MgX

O MgX

CH3

CH2C6H5

CH2CH2OH

2--1

(CH2=CHCH2MgX)
.
.
( ,-
), 1,2- 1,4-:

R"
R' CH CH C O + RMgX
4

1,2-

R"

1,4-

CH CH C OMgX

R' CH CH C OMgX
R

R
H3O+

R"

R'

H3O+

R"

R'

R' CH CH C OH

R"
CH CH2 C O

, 1,2-,
1,4-.
(I) , 1,4- (.
14.1.5.). . ,

1500

1501
, - (VIII) 1,4-,
,- - 1,2-.

C6H5
C6H5CH C C C6H5
O

(C6H5)2C CH C C6H5
O
,-

C6H5

1. C6H5MgBr

(C6H5)2CH C C C6H5 (100%)

2. H3O

1. C6H5MgBr
+

2. H3O

C6H5
(C6H5)2C CH C C6H5 (100%)
OH

19.2.3.6. -
( 19.1.4.6)
, , , 2, ,
.
.
. , .
, - ,
.
H3O+

CH2H

RMgX

R-CH2-OMgX
RCH2OH

+
R
H3O
R'CH=O R
C OMgX
C OMgX
R'
R'
R'R"OH

R
R' C OMgX
R"

H3O+

R
R' C OMgX
R"

,
, .
-M () ,

- . 1,3-
:

1501

1502

CH

R'
R'C-CH2-CR' + RMgX
O

RH +

R'

XMg
, . ,
.

C
H

MgX

H
MgX
R2C O

R2C O

R2CH OMgX

,
:

R'
R'

R'

C O + RMgX

R'

C O MgX + R

(-)

(19.12)
1/2 R'2C OMgX

R'2C OH

H3O

R'2C OMgX

R'2C OH

,
, :

2Ph2CO + 2CH3MgX

[Fe]

(Ph2COMgX)2 + CH3CH

,
,
.
, , .
20%- ,
,
SET- ( 19.12; R = (3)32, R = C6H5).
-
( , R = CH3 -49),
- :

Ph2CO

+ C6H4(NO2)2

Ph2CO + C6H4(NO2)2

(19.13)

. , , RMnX =

1502

1503
. , 1,2-:
1,2-.
+

>C O

>C

R MgX

>C O

R MgX

MgX

- SET- 1,2-
. ,
,
"", (..
). ,
, .. .
,
( 19.13)
. ,
( ).

1,2-.
S- 1.2-.

R'2C O

R'2C=O + RMgX

MgX

R'2C O
R

OMgX

R'2C=O + RMgX

R'2C(R)

MgX

R'2 C OMgX
R'2 C OMgX
R'2C(R)

+ RH + R2 + R-H

OMgX

,
, -, ,
, .
, ,
, ,
,
.
. RCOX ( =
O-, NR2, OR, OCOR, Hal)
( 19.1.4.).

1503

1504

R'COO

RCOR' + R'2RCOH

R'CONR" 2

RMgX

(R'CO)2O

R'COCl

RCOR' ( + R'RC(OH)NR"2)
RCOR' + R'2RCOH
RCOR' + R'2RCOH

, , , ,

Rg.
RRC(OH)NR2 R2NH,
RCOR.
, ,
,
, .

oo

( 19.1.4.6) C=S

"" .

R'2C=S + RMgX

R'2C-SR

H3O+

R'2CHSR

MgX
. 2,
.
, ,
Rg , .
==
: (R2==O), (RN=C=O), (RN
=C=S), (S=C=S):
CO2
R'2C=C=O

RMgX

R'N=C=O
R'N=C=S
CS2

RCOOH

( )

R'2CHCHR

()

R'NCOR

()

R'NCSR
S
RC SH

()

1504

( )

1505

19.2.3.. -

.

R'

R'

C N + RMgX

C NMgX

R'

H3O+

C O

,
, , -
.

RMgX .
,
, , :

CH3OCH2C N

-C4H9

-C4H9MgBr

CH3OCH2C=NMgBr

-C4H9Li

-C4H9

-C4H9
MgBr
CH3OCH2-C-N
Li
-C4H9

CH3OCH2-C-NH2
-C4H9
5--5-

R'
R

R'

C NMgBr + R'C N

R'
C N

C NMgX

R'2C=NR" + RMgX

R'2C NR"
R MgX

R'2C NR"
R H

R'2 C NR"2 + MgX2

R'2C=NR'2 + RMgX

,- ,
. ,
1,4-:

1505

1506

H
C

Ph + PhMgBr

Ph
C

NPh

Ph

Ph

H3O+

CHPh
NHPh

Ph NMgBr

-2-

( )
, :

CH3 CH3
6H5MgBr + C6H5CH-C=NOH

CH3

CH2

C6H5CH C

NH + MgBrOH

C6H5
,
.

2:

+ CH2=CH(CH2)nMgX
N

H
N
MgX

H
N

(CH2)nCH=CH2

2-

(CH2)nCH=CH2

(CH2)nCH=CH2

19.2.3..

-.
(, Ni, b, g, F). -
.
, ().

R'X + RMgX

CoCl2

R-R' + MgX2

; ,
- -,
. ,

:

1506

1507

II

Co

Cl

II

Co

Cl

II

Co Cl2 + RMgX

+ MgXCl

Co0 + RCl

-g -
( ):

MgX

II

Co0 + RMgX

Co

Co0 + R'X

Co

R
X

II

R'

:
II

Co

II

Co

Co

+ RMgX

Co

MgX
R'
X

II

+ R'X

R'
II

R'
R

+ MgX2

+ MgX2

II

Co

Co0 + R-R'

R'

,
:

RMgX

RR'

R'X

RR'

M0

M0
R
M

II

R'

R'
M

II

MgX2

II

R'

1507

M
XMg

MgX2

RMgX

R'

R'X

II

1508
.
L2NiCl2
25oC

C2H5MgBr + C6H5Cl
C6H5MgBr + F

Pd
25 oC

C6H5C2H5 (98%)

(92%)

-
Fe
0 oC

-C6H13MgBr + CH2=CHBr

RMgBr +

Br

R'

1-

Fe
25 oC

CH2=CH(CH2)4MgBr + CH2=CHBr

RMgBr + R'

-C6H13CH=CH2 (83%)

CH2=CH(CH2)4CH=CH2 (64%)
1,7-

R'

R ( Z-

R'

Br

( -)

19.2.3..

, R(OR)2
.

O
RMgX + CH2

RCH2CH2OMgX

CH2

H3O+

RCH2CH2OH

RMgX +

O CH2
CH2 CH2

RCH2CH2CH2OMgX

H3O+

RCH2CH2CH2OH

.
,
, , r, lkO:

CH3CH

OAr
OAlk

CH3CH

+ RMgX

R
OAlk

+ ArOMgX

, 1,3- (VIII)
, .

CH2
R' CH
O CH2

1508

XVIII

1509

:

RMgX + HC(OC2H5)3

H3O+

RCH(OC2H5)2

RCHO

19.2.3..
, .19.1.
.
-, NH-, SH- C-. , ,
, , ,
, , .

RMgX + HY

RH + MgXY

Y = OH, OR', SR', NH2, NHR', NR'2, R'C

C ..)

,
, :

RC

RC

CH + CH3MgX

C-MgX + CH4

C6H5CH2COOH + 2(CH3)2CHMgCl

C6H5CH-C
Mg

O
OMgCl

. .
- ,
. (. 19.1.4.).
.
.
- . - , .

R'

N O + RMgX

R
R'

N OMgX

H3O

R
R'

N OH

,- 1,4-.

, , 1,3,5-:

1509

1510

O N OMgI
H
CH3

NO2
+ CH3MgI
O 2N

IMgO

NO2

CH3
H3O+

CH3
O
N

O CH3 H

OMgI

H NO2
H

H
O 2N

CH3

H
H
NO2
CH3 H

1,3,5--2,4,6-

19.3.

l(III)

""

.
, ,

.
, ,

, ,
:

R3Al + 3H2O

2RH + Al(OH)3

3R3Al + 3O2

2(RO)3Al

:
RAIX2, R2AlX R3Al, R - , , -,
(, N), , R, SR, NR2 ..

19.3.1.

:

CH3

X
Al

Al
X

CH3

CH3
CH3

: = OR > NR2 > SR > PR2 > Hal > Alk.

,

1510

1511
l , (=lk),
.
( 1V .19.1.2).
R3Al , -, R.
: 3 > C2H5 > -37 > -C3H7. , R. , R
, . ,
R2l=R , 100 oC.
CH=CHR.
, ,
, -o
, .19.1.
- R2AlH (R = Et, i-Pr)
.
- , l (III)
: ,
, , ..
,
. t3Al Me3N > 3P > 2O
> Me2S .

c
, . , ,
,
.

19.3.2.
,
( 19.1-19.6),
RAlX2 R2AIX. ,

- :

3RX + 2Al

R2AlX + RAlX2

NaX

R2X + Na [RAlX3]
"a-"

R2AlX RAlX2
a-,
.

1511

1512

- ( 7:3):

Al2Mg + 4RX

2R2AlX + MgX2 (R = CH3, C2H5)

R3Al AlCl3:

2(-C6H13)3Al + AlCl3

3(-C6H13)2AlCl

2(-C6H13)3Al + AlCl3

3 -C6H13AlCl2

(C6H5)3Al + 2AlCl3

3C6H5AlCl2

hCM -, :

(C2H5)3Al + HCN

(C2H5)2AlCN + C2H6

,
( -),
, ,
.

-,

. .

2Al + 3Hg(CH2CH2CH=CH2)2

2Al(CH2CH2CH=CH2)3 + 3Hg

(-C4H9)3Al.OEt2 + 3MgCl2

3 -C4H9MgCl + AlCl3
3 -C3H7Li + AlCl3

(-C3H7)3Al + 3LiCl

19.3.2..
,
,
- ( ), , Et2AIH (i49)2l ( -) .

4R3Al + 3H2 + 2Al

6R2AlH

[(CH3)2CHCH2)]3Al

100 oC

[(CH3)2CHCH2]2AlH + CH2=C(CH3)2

(>95%)

,
- .
, .. ,
.

1512

1513

19.3.2..

. R2AlCH2CH2R

(

),

, .
R2AlCH2CH2R
.

R2AlH + CH2=CHR'

R2AlCH2CH2R'

2R2AlCH2CH2R'

RAl(CH2CH2R')2 + R3Al

2RAl(CH2CH2R')2

Al(CH2CH2R')3 + R2AlCH2CH2R'

,
. ,
:

i-Bu3Al + 3C8H17CH=CH2

(C8H17CH2CH2)3Al + 3CH2=C(CH2)3

: RCH=CH2 > R2C=CH2 >

RCH=CHHR.
1-, ~ 100
.

[2,2,1]

(XIX)

, (XX) R2Al- .

XIX

XX

i
(1V), Zr(1V), .
.
-1 ,
.
.

AlkCH=CH2

C6H5CH=CH2

97%

25% 75%

3%

1,1- (XXI) -.
D2 -2,3--1,1- (II).

1513

1514
(..20),
- II , - l-D.

CH3 CH3

CH3

i-Bu2AlD
Et2O, 60 o C

H
H

XXI

CH3

CH3

XXII

D2O

H
AlR2

CH3

XXIII

H
D

,
, ( 6.3.2, . 3), .. .


,

..

.
,
.
(. . 6)
-, ..
.
, -. ,
-1 - ,

D2

90%

10% -1 .
-C4H9

-C4H9C

CH + RAlH2

60 o C, 4

H
AlR2

-C4H9

D2O

(`90%)

1-D--1 1,1-, ,

-C4H9 C CH + R2AlH

-H2

-C4H9C

1514

CAlR2

D2O

-C4H9 C CD

1515

-C4H9 C CH + 2R2AlH

-C4H9CH CH(AlR2)2

-H2

D2O

-C4H9CH2CH2D2

, , 1-, ,
5%, 1-, 28%.

,
- :
-BuC

CH + R2AlH

Et2N; 20 oC
-H2

-BuC

CAlR2

R2AlH
70 oC

-BuCH2C(AlR2)3

1,1-:
-BuC

CH + R2AlH

-BuCH2CH(AlR2)2

.
-

1,2-

,
Al-H
.
R2l 1,2-
, ,

.
-C6H11C

i-Bu2AlH
(-C6H11)2BH

CH3

-BuC

CH3

25:75

15:85

9:91

3:97

19.3.3.
,
.19.1. .

1515

1516

, :

CH3
CH3

C CH2

CH3

1. R2AlH

CH3

2. H2O

CH CH3

.
-.

(CH2)6

1. i-Bu 2AlH

CH2

C C CH2 2. CH3OH

CH2

CH2
H

Z-
1. i-Bu 2AlH
(3 )

C C CH2 C C(CH2)8Cl

C C

-Bu

(CH2)6

-Bu

CH2
C C
C
H
H H

2. CH3OH

C-Al

(CH2)8Cl
H

(.20) .

1-

:
H3C

CH3

H3C
1. i-Bu2AlH
2. O2
3. H2O

H3C

CH3

OH
H3C

1516

CH3

CH3

Z,Z-

1517

.
-C4H9 C

C2H5C

CH

-C4H9
1. i-Bu2AlH
2. Br2,
H
3. H2O

C2H5

1. i-Bu2AlH
2. I2
3. H2O

CC2H5

Br

.

,

-,

- .
R3Al + R'Li

[R3R'Al]Li
a-

1. R''CHO
2. H2O

R''RCH2OH

1:1,

.
, . ,
- , .

.
(C2H5)3Al + C6H5C N

150 oC

C6H5
C6H5

C NAlEt2 +
H2O

C6H5
C6H5

1517

C O

C6H5
H

C NAlEt2
H2O

C6H5CH=O

1518

.

.

( -78).
.
.
OH
H

O
2 i-Bu2AlH
, -60oC

92%

HO

O
OCH3
OCH3

1 i-Bu2AlH

OCH3
OCH3

, -78oC

COOCH3
RCONR'2

CHO

1. 2 i-Bu2AlH2
2. H2O

RCONR'C6H5

RCH2NR'2

1. 1.5 i-Bu2AlH
RCHO
2. H2O

.
: < < .
, ,

(C2H5)3Al + (CH3)3CCl

[(CH3)3C Al(C2H5)3Cl]

(CH3)3C-C2H5 + (C2H5)2AlCl

- ,
.
1518

1519

-C6H13

SiMe3 CH Li
3

-C6H13

AlR2

SiMe3

-C6H13

CH3I

AlR2(CH3)Li

(R = -C4H9)

, , .

"a-"

, :
H

Br
-Bu

NiL4

Bu-

AlR2
(R = -C4H9; L = P(C6H5)3)

( 19.3.2.),

.

19.4.
(II) ( , ,
)
-. ,
, ,
(, ..),
, , , ,
(

R3),

,
. ,
, , -
,

1519

SiMe3
CH3

1520

.20,

.
- . ,
(3)2Hg CH3. + CH3Hg. 51
/.

,
.

19.4.1.

:

R2Hg

( ) RHg ( = Hal, NO3, 3, R',

..).

- .
RHgX -
.
RHg+
X-, X-.
RHg+ (
3.2.1), , RHg
X- (F > Cl >
1520

1521

Br > I).

(X=Hal)
- .
R-m + HgX

RHgX + mX

2R-m + HgX

R 2 Hg + 2mX

(m = Li; MgX)

(
19.4.2)

, :
RHgX + CHCl3 + t-BuOK

RHgCCl3 + t-BuOH + KX

-,

:
C6H5C

CH

OH

C6H5C

HgI42

(C6H5C

C)2Hg

-()

C 6F 5H

HgI42
OH

(C6F5)2Hg

()

.

, :

CH2=CH-CH2I + Hg

CH2=CHCH2HgI (, 1855 )
+ Hg

N
CH3 CH Br

CH COOC2H5 + Hg
Br

CH3 CH HgBr
8-(1-)

8-(1-)

(~100%)

0.5 , 20

0.5-2 , 20

(X = Alk, Hal, NO2)

1521

CH COOC2H5
HgBr

(70-90%)
-

1522
,
" ", , -:

6Br5CH2Br + Hg

3 , 20

2C6Br5CH2HgBr + 2Br

C6Br5CH2HgBr

(C6Br5)CH2)2Hg + HgBr42

-() (~100%)

.
:

CH3I + Hg

CH3HgI

(). (.
13):
- -:

C6H6 + Hg(OAc)2

AcOH
100

CH3

C6H5HgOAc

CH3

CH3
+ Hg(ClO4)2

( )

HgClO4
+

HClO4
25

CH3
+
HgClO4
HgClO4

(7%)

(19%)

(74%)

,
. ,
(~40% -, ~40% - ~20%
-). ,

H2 N:

NH2
+ Hg(OAc)2

H2O
20

OAc
Hg OAc

NH2
HgOAc

( )

1522

1523

+ Hg(OAc)2

150

O: Hg OAc
C
O
AcOHg

( )

,
KI r2, :

HgOCOCF3
+ 6Hg(OCOCF3)

F3COCOHg

HgOCOCF3

F3COCOHg

HgOCOCF3
HgOCOCF3

I
KI

I
I

,
gX2 .
...

ArN2 X

+ HgX2

ArN2 HgX3

Cu

ArHgX + CuX + N2

ArN2 HgX3

Cu, NH3

Ar2Hg + CuX.NH3 + N2

, XXI.
(
-)
II, (
19.4.3).

X
+ HgX2

XXI

HgX

1523

1524

Y
+ HgX2 + HY

XXII

HgX

-, , ,
,

-.

OH
Hg(OAc)2, /H2O

CH3CH-CH2HgOAc
OH

Hg(NO3)2, H2O/OH

CH3CH-CH2HgNO3
OR'

Hg(OCOCF3)2, R'OH

CH3CH=CH2

CH3CH-CH2HgOCOCF3
OOR'

Hg(OCOCF3)2, R'OOH

CH3CH-CH2HgOCOCF3
NR'2

Hg(OAc)2, R'2NH

CH3CH-CH2HgOAc

( ; . 5.4.3.)

N3
+ Hg(OAc)2 + NaN 3
HgN3
-2-

RC

CR'

1. Hg(OAc)2
2. NaCl

R
AcO

HgCl
R'

19.4.2.

19.4.2..
Y

1524

1525

,
, p.
.

.
HgX2
HY

RCH=CH2

HCl NaBF4

RCH-CH2-HgX
Y

RCH-CH3
Y

, .
. , in
situ. .

19.4.2.6.
-

.
AlBr3 , ,
:

Cl
(CH3)3CH=CHHgCl + CH2=CH-CH-CH3

Li2PdCl4

(CH3)3CCH=CH-CH2-CH=CHCH3

,
, :

2RCH=CHHgCl
2ArHgX + Cu

PdCl2
LiCl
PdCl2

1525

RCH=CH-CH=CHR
Ar-Ar + Hg + CuX2

1526

, , CuCl2
:
PdCl2

RHgX + CH2=CHR'

RCH=CHR'

PdCl2

ArHgCl + CH2=CHR

ArCH2-CHR

CuCl2

Cl

, -,
(.21). ,
, - .

.
.

CH3CCH2HgCl + CH3COCl

CH3C=CH2 + HgCl2

O-COCH3

lBr3
, :

R2Hg + R'COCl

AlBr3

RCOR' + RHgCl

19.4.2..

:
RCH=CH2

HgX2
Y

RCH-CH2HgX
Y

Hal2

RCH-CH2
Y

Hal

,
. ,
,
(.. 20),

1526

1527

,

, ,
..

19.4.2..
- RHgCXYZ

. . :CYZ,
(..5).

R Hg

R-Hg-X + :C

>

<

Z, ,
,
RHgCXYZ. .19.2
.
19.2

Hg(CH2X)2 (X=Cl, Br)

:CH2

PhHgCBrClI

:CBrCl

PhCH2HgCH2I

:CH2

PhHgCCl2I

:CCl2
:CCl2

PhHgCHBrCl

:CHCl

PhCH2CH2HgCCl3

PhHgCHBr2

:CHBr

PhHgCCl2Ph

PhHgCCl2F

:CClF

PhHgCBrClCOOR

:CClCOOR

PhHgCCl2SO2Ph

:CClSO2Ph

:CClPh

: I > Br > Cl > F (. 19.2);

. , R = lk,

.

19.5.

1527

1528

19.5.1.

,
(, ).

RX + Zn
2RZnX

RZnX

R2Zn + ZnX2

(X = I, Br)

( )

R2Zn ,
, RZn (X = , OR, NR2, SR, PR2)
Zn--Zn.

-
.
,
.

- :

+ Zn/Cu + CH2Cl2

+ ZnI2
[4.1.0]

:2 , -,
III.
CH2Cl2

ICH2ZnI

ZnI
CH2

CH2
XXIII

1528

ZnI
I

CH2 + ZnI
I

1529

ZnI2 + CH2N2

Zn(CH2I)2 + N2

(73%)

+ Zn(CH2I)2

+ (C2H5)2Zn + CH2I2

(79%)

+ (C2H5)2Zn + CH2ClI

(99%)

C6H5

+ (C2H5)2Zn + C6H5CHI2

(64%)

Ar
(30%)

(E)-ArCH=CHCOOC2H5 + Zn/Cu + CH2I2

COOC2H5
O

(90%)

+ Zn/Cu + CH2I2

OH

OH + Zn/Cu + CH2I2
4-

(33%)

-3-[3.1.0]

-
- , - .

1529

1530

R
R'

H2O

C O + Zn + BrCH2COOC2H5

OH

C CH2COOC2H5 + ZnBrOH

R'

R
R'

C CHCOOC2H5

,

.
R''CHO
R''2CO

R''2C(OH)CRR'COOEt

R''COCl

BrCRR'COOEt

R''CH(OH)CRR'COOEt

R''COCRR'COOEt

R''CON
R''2C=CHCOR'''
ArCH=NAr'

R''COCRR'COOEt
R'''COCH2CR''2CRR'COOEt
ArCH(NHAr')CRR'COOEt

, .
BrCRR'CONR''2 + R'''CHO + Zn

BrCRR'CN + R''CHO + Zn
BrCH2=CHCOOEt + RCHO + Zn

R'''CH(OH)CRR'CONR''2

R''CH(OH)CRR'CN
RCH(OH)CH2CH=CHCOOEt

(,

BrZnCH2COOEt),
.
,
.

1530

1531

19.5.2.

: R3Tl, R2TlX RTlX2. IIIA
. ,

,
l(III).

.

R2TlX, ,
R2Tl+ (II) R2Hg (.. R2Tl+ R2Hg
). R2Tl+
R2Hg

-
, l (III)
l(I).
RTlX2

RX + TlX

, , ,
.
,
.
-
(III) -
.

(III)

.
,

R2TlX

1531

1532

2RMgBr + TlBr3

R2TlBr

-MgBr2

R3Tl + LiBr

RLi

(R = ,
80%)

R2TlX
RMgX:

3RMgBr + TlBr3

R3Tl + 3MgBr2

TlI CH3I
:

2CH3Li + CH3I +TlI

(CH3)3Tl + 2LiBr

( ) TlI 3I,
:

CH3I + TlI

CH3TlI2

CH3Li

(CH3)3Tl

(.21).

()

) ()
, , , ..

Ar-m + TlX3

ArTlX2

(m = B(OH)2, HgCl, Si(CH3)3, Sn(CH3)3; X = Cl, Br, I, CF3COO)

III)

Ar-H + Tl(OCOCF3)3

CF3COOH

ArTl(OCOCF3)2 + CF3COOH

- -,

1532

1533

-. :

CH3

CH

CH3

CH3

CH

CH3

CH3

20 oC

73 oC

Tl(OCOCF3)2

CH3

Tl(OCOCF3)2
()

()

CH

()

. ,
,
,
-
-. ,

-.
(-
)

-:
CH3O

CH3O

Tl(OCOCF3)2

CH3O

O
Tl(OCOCF3)2

+ Tl(OCOCF3)2

-

.

1533

1534

(CH2)nCOOH

(CH2)nCOOH
IC6H4(CH2)nCOOH
(-, - -)

Tl(OCOCF3)2

+ Tl(OCOCF3)2
n

95

92

29

13

10

58

84

86

-, -,
,
-:
O

OH
(CH2)n

(CH2)n

C
O

Tl (OCOCF3)3

H
-CF3COOH

COOH
O

Tl (OCOCF3)2

Tl(OCOCF3)2
+

-H

( =0) ( =2)
KI -,
- ;
29% -, ..

, .. , 5- 6 .
-
.

C6H5(CH2)nOCH3

1. Tl(OCOCF3)3
2. KI

, -:

1534

IC6H4(CH2)nOCH3

1535

(CH2)n

CH3

% -

% -

Tl (OCOCF3)3

% -

93

99

85

12

27

67

,
. , I2 KI (
) :
CH3

CH3

CH3

1. Tl(OCOCF3)3, CF3COOH
2. KI, H2O

Tl I +
CH3
I

COOH

COOH
1. Tl(OCOCF3)3, CF3COOH
2. KI, H2O

OCH3

I
Tl I +
OCH3

OCH3

NO2

1. CH3COONO2
2. I2

Tl(OCOCF3)2

CH2COOH

CH2COOH
CH3

CH3

1. Tl(OCOCF3)3, 20 o C
2. KI, H2O

1535

1536

CH3

CH3
1. Tl(OCOCF3)3
2. KI

CH3

CH3
I
Cl

Cl

Cl

Cl
1. NaOH
+
2. H3O

1. Pb(OCOCH3)4
2. KI

OCOCF3

Tl(OCOCF3)2

OH

in situ ,
.
.
, - 2--4-
C-Tl, .
(.. 100%).

CH3

CH3

Br
C6H6

Br

Br

CH3

CH3

Br

Ph

Tl(OCOCF3)2
CN, NH2, SH .

Cl

Cl

Cl
h
H2O, KCN

Tl(OCOCF3)2

Tl (CN)3

CN
(III)

.
( 19.4.2), IV,
,
.

1536

1537

>C

>C C< + TlX3

OR

ROH

C<

>C C< + HX

3+

Tl

X2Tl
XXIV

- ,
, ,
, -, .. ,
.
-
-, -
( ), ,
. ;
.
, .

+ Tl(OCOCH3)3

OAc

CH3COOH

CH(OAc)2

+
OAc

(30-40%)

(40-50%)

HO

1. Tl(NO3)2, CH3OH
+

2. H3O

CH3

Tl(ClO4)2

1-

COCH3

l (III) ,
g (II), :

CH

Tl(NO3)3

H
RC C
HO

Tl(NO3)2

H2O
-Tl(NO3)3

C CH2OH

Tl(NO3)3

RCOOH (~ 80%) + CH2=O + Tl(NO3)

():
+

C6H5C

CC6H5

Tl(NO3)3, H3O

C6H5

C C6H5

O O

1537

1538

19.5..
: ,
, , SnH4 - .
(CH3)4Sn , (CH3)3SnCl ..
, (, , ),
.
: R4Sn, R3SnX, R2SnX2
RSnX3, R - , - . 3
(.20) R3SnR, R R'
, , ,
- R R'H.
, , , ..

..

RRRSn ()
RR'RRSn , RR'RSnI
.
,
:
R3Sn

SnR3

(R2Sn)x

R2+x Snx

(, = 9)

, :
R4Sn << R3SnX < R2SnX2 < RSnX3 < SnX4

, , R3SnCl.L, R2SnCl2.L2,
RSnCl3.L2

, L - ( ),

, .
,
.

1538

1539

,
,
..
RSn3 R2Sn2 ,
R3SnX , , -
.

.., .

(IV) .

SnCl4 + R-m

R4Sn + 4m-Cl

(m = MgX, Li, Na, K, Al<, ZnBr; R = , , , )

R4Sn ,
, .
:
/

SnCl4 + 4C4H9Cl + 4Mg

Bu4Sn + 4MgCl

3Bu4Sn + 4[AlCl3.NR3]

4Bu3Al + 4R3N + 4SnCl4

, ,
, (>=, -N) ()
(-OH, -SH, -NH2) , .. -, . ,
,
.
.

(-C4H9)3SnH + CH2=CHC

O
OCH3

Ph3SnH + CH2=CH-OCOCH3

Et2SnH2 + CH2=CH-CN

(-C4H9)3SnCH2CH2COOCH3
-())

Ph3SnCH2CH2OCOCH3
2-

Et3Sn(CH2CH2CN)2
-(2-)

CH3

CH3
-BuSnH3 + CH2=CCOOCH3

1539

-BuSn(CH2-CCOOCH3)3
---(2-)

1540

- .

--

() ():
CH3
N

CH3

C C N N

t o h

C C N

CH3

N2 + 2 C(CH3)2CN

CH3

--() ()

R3NSnH + C(CH3)2CN

(CH3)3CHCN + R3Sn

R3Sn + CH2=CHR'

R3SnCH2CHR'

R3SnCH2CHR' + R3SnH

R3SnCH2CH2R' + R3Sn ..

4Bu3SnCl + LiAlH4

4Bu3SnH + LiAlH4

2Bu2SnCl2 + LiAlH4

2Bu2SnH2 + LiAlH4

,
.

O-...

n/2 (Bu3Sn)2O + (CH3)SiO( Si-O)n-Si(CH3)3

nBu3SnH + (CH3)3SiO-(Si-O)nSi(CH3)3

CH3

CH3

n/2 Bu2SnO +

n/2 Bu2SnH2

,

.

.
:

R3SnH + R'X

R3SnX + R'H

(R' = , ; X = F, Cl, Br, I)

:

R3SnH +

R3Sn
1540

1541

:
R3Sn + R'X

R3SnX + R'

R' + R3SnH

R'H + R3Sn , ..

, , .
R3Sn
I > Br > Cl >F,
, , :
> > ,
.

, , -,

( ), -,
-, , -,

, ,
= =.

.
:

R3Sn + R'C
R3SnH

R3SnX + R'-C=O

R'CH=O ()

R'C=O
R'CHO

R'C

R3SnH

O-CHR'

R'C

+ R3Sn
O-CH2R'

, =.
R3Sn

+ >C=O

>C-OSnR

1541

1542

>C-OSnR3 + R3SnH

>CH-OSnR3 + R3Sn
H3O+

>CH-OH
()

(IV) 200.
R4Sn SnX4

R4Sn + SnX4

20

R3SnX + RSnX3
( )

200 oC

3R4Sn + SnX4

200 oC

R4Sn + SnX4

4R3SnX
2R2SnX2

,
200 oC

R4Sn + 3SnX4

4RSnX3

- ,
.

;
C-Sn
( ):
R4Sn + X2

R3SnX + RX

R3SnX + X2

R2SnX2 + RX

(X = Cl, Br, I; X2: Cl2 > Br2 > I2)

r2 0 -50 , I2 -
( ~ 70

C ).

() ,

, ,
..). -
. 20.

1542

1543

19.6.

-

-
( ) . ,
,
, ,
.
, , , ,
, - SET (. 19.1, 19.2, 19.).
, ,
, , -
, - .

,
, , , , ,
,
( ) (

,
.
, -,

, ; R-Hg
R-Sn

. .3 ( 3.3)

() -.
, R,
- -
- .
,
,

1543

1544

.
, R3SnCH2Z , Z, N,
R, COOR . ., ZCH2- ( 3.5.3.3.,
. 3),
(. 19.5.1). .

Bu3SnCH2CN + C6F5CHO

C6F5CH(CH2CN)OSnBu3

(COOH)2

C6F5CHCH2CN
OH

Et3SnCH2COCH3 + C6H5CHO
(COOH)2

C6H5CH(CH2COCH3)OSnEt3

C6H5CHCH2COCH3
OH

Et3SnCH2COOEt + CCl3CHO
(COOH)2

CCl3CH(CH2COOEt)OSnEt3

CCl3CHCH2COOEt
OH

CH2Z , u t, .. ,
-.

, ,
, ,

, ,

-,

,
,
(,

19.1).

. ,

. , -

1544

1545

-,
HCl, -
, .

C6H5SO2CH2HgCl + I

C6H5SO2CH2Hg ClI

H2O

C6H5SO2CH3 + HgClI + OH
- , -.

1545

1546

20

20.1. ......................................................................................................... 1546
20.2. ............................. 1548
20.2.1. ..................................................... 1548
20.2.2. .............................................................. 1549
20.2.3. ......................................................................................... 1553

20.3. -..................................................................................................... 1555

20.4. ........................................ 1559
20.4.1. .............................................................................................. 1560
20.4.1.. SE2 ............................................................................................................. 1562

20.4.1.. SEI ................................................................................................................. 1565

20.4.1. SE1(N) ............................................................................................................. 1568
20.4.1. . S' .............................................................................................................. 1574
20.4.1.. - ........................................................................................................... 1575

20.4.2. .......................................................................................... 1577

20.4.2.. ........................................................................................ 1581
20.4.2.. .............................................................................................................. 1585
20.4.3.. 1594

20.5. -1599

20.1.

S :
R-Z + E+ R-E + Z+
+ - () ,
(, H3O+),
(HgCI2) (F3-).
Z + ;
,
,
. , ,
- , , Z= HgCI, HgR, SnR3,
1546

1547

AuR2, PPh3. ,
- .

,
. , --
-,
:
CH3CN
CH3

C C N N

NO2

CH3CN

60 o

CH3CN
CH3

C C

NO2

N N

CH3CN

(.. ) ,
o ;

CH3
NC C
Ar
CN

CH3

CH3

CN

CH3CN

Ar

25 o

C
CN

CH3

CH3
CH3

, ,
, , .
R'
R
E

C O

R'
R'

C O

R'

1547

1548

20.2.
20.2.1.

SN ,
SE2 ,
SEl.

SE1: R-Z

R + E

SE2: R-Z + E

+ Z
R-E

(20.1)

+
+
E.....R.....Z
R

Z
E

R-E + Z

(20.2)

, Sl
R-. , Sl-

. 3 -
, SE1-
.
SE2
( 20.4),
( 4.10).
, ,
, . , (20.1)
(20.2) SE1- SE2-;
,
, . S- .

(. 20.2.3). ,

,
.

1548

1549

20.2.2.

Sl,

. . Sl ,
, , ,
COR, H, NO2, N, Ph, =2 ..,
.

.
:
E

E
Z
a

-Z

E
-

()

, -, ,
, . 3, ,
, , (. 3,
), :
a

a
b

Z
c

-Z

a
bc

a
c

a
E
c

, (..
)
Sl-.
,
1549

1550

. , Sl-,

SN1 (..9),
,
.
,
, ,
:
R
ArSO2

R'

Ar

C
R'

(

)

SEl-
.
SEl-
,

.
,
. ,
,
(., 1968).
SE1 :
Me
Ph
Et

R
C O
R

Me

Me
Ph
Ph

Et

C H + A
Et

( - , )

, 2-,
99% ( )
60% ( )
( ).
(, ) - ,
:

1550

1551

H A

Ph

Me

O M

Me

Me
H A

CR2

Ph

Et

Et

Ph
Et

CR2

, .

(,

H2222)
(), ()
.
:
Me
Ph
Et

O H

Me

B M

CR2

O
CR2

A H
Ph

Me
H

Et

Ph
Et

()
,
,
.
( - , - , - )
SE1-, ,
(-) - (. 20.3).
, SE1-
, ,

, .
S2,
(20.2). . 9, SN2,
, S2

1551

1552

, .
,
-Z,
.
Z

E+

E+

(I), a -
() ;
, -
C

Z ()

()

(II)

(I)

. ,

SE2-

(CH3)3CCH2Z, SN2-
- .
, , ,

-C4H9Sn(-C5H11)3 + Br2

-C4H9Br + (-C5H11)SnBr

, o-,
.
I
, II, Z
,
II I. -

1552

1553

(. 20.4.2.),
.

20.2.3.

S-
,
(20.1) (20.2), , ,
.
: (I) "" Nu-,
-Nu (, l- HgCl2 ( = HgCl+) , r- Br2
(E=B+) , I- I3- (=I+) ..; (2)
(, , , ..) (3) ""
,
(, -
-).
( 20.4.1.)
(20.1) (20.2) - .

, , ,
.
.
, -,
Sl-,
-,
.
, ,
, Sl, S2 -.
.
S1(N),
SEi. SEi

1553

1554

III,
- M-Nu E-Nu -
, .. .
S1(N) SEi :

SE1: R-M + Nu
R-M-Nu
R + E
:

R + MNu

R-E

( )

R-M + E-Nu

R-M-Nu

R M
E Nu

R M

R M
E Nu

E Nu

R + E Nu M

R-E + MNu

( )

SEi:

R M
+

E Nu

R M

E Nu

M
Nu

(III)

(-Nu - , () (Nu) ).

SE2,
, , :
R M Nu

R M + Nu
R M Nu

M Nu

SE2(C) (.. SE2 ),

SEl - .
SEi .
SE2 . ,
,

1554

1555

, -
III, ..

c ,
.

SE1
SE1(N)

(, ,

SE2 ( )
SEi

SE2 ( )

20.3. -

, , .

:
R-H + B-

R-.....HB

DB

R-.....DB

R-D + B-

(20.3)

(, - = ND2-, DB = NH3 .; B- = t-BuO-, DB = t-BuOD, ; B- =

DO-, DB = DOD, D2 ..).

-,

o , , -,
- (. 3, 3.5.1).
SE1(N), ..
- . -
,
SN2- .
(20.3)
, , - .
, ,
, Et3N ()-D2O CH3OD ().

1555

1556

KND2/ND3 (.) S/t-BuOK/t-BuOD.

, SE1(N):
R-CH2-CH=CH2 + B

R CH

-BH

R-CH=CH-CH3

CH CH2
HB

-B

(R=Ar) (R = CH2=- ).

:
CH3
HB

+ B

(. .
10.2.3), .. ,
(
).

.
,
:
R CH2 C CH

+B
-BH+

RCH

RCH C CH2
()

CH
RC

RCH C CH
C CH3

B ,
; , , , ,
()
, :

1556

1557

R C C CH3 + B M

RC

CH2

R C C CH2
RCH2

R CH C CH

R CH C CH

C C M

- +

(, B = NH2CH2CH2NH K )

(. 17, 17.1.3).
,
. S1(N)
- .
, (.
. 17, 22).

B

C CH2 C
O
O

CH

+ ArN2

O
C O

C O
C CH N NAr

C C N NHAr

R2CH C

+ HNO2

O
RCH2

+ HNO2

R2C C
O N O
R CH C
N O O

C C O
N OH

1557

1558

C O
C CH2

C O

B
+

-BH

C CH

+ N N N

O
C O
C C H N
O N N

Ts

(Ts = n-CH3C6H4SO2)

C O
C C N N + TsNH

Ts

BH

TsNH2 + B

SE1(N)-, N -
, .. .
SE2
. , SE2-,
( ) -

(5+)

(,

, 5+ -):
CH3

H + D

1
(-1)

H
C
H
D
H

2
(-2)

CH3

D + H

(-3) 3

CH3 + HD
: (-1)
, (2) - , (3) -
HD. -
. 4 CH3D ,
, 4,
- :

1558

1559

H3C

CH3 + CH4

CH4

H3C

CH(CH3)2

CH3CH2 + H2

CH4

CH2CH2CH3

(CH3)2CH

H3C CH2

CH3

CH2 CH2CH3

-H2

CH2CH(CH3)2

H3C

CH2CH(CH3)2

H
CH2CH3

CH3C(CH3)2
()

, --


.
> > .
SE2- .

20.4.
, - -,

SE-, SN-.
,
-, -
: ,
, , , ..
. 19,
,

,
:
R-M + H-Nu RH + MNu

()

R-M + Hal-Nu RHal + MNu

()

1559

1560

R-M + M-Nu RM + MNu

( )

, ,
, .
. ,
, , R2Zn , R2Cd, R2Hg ,
HCl.
.
-
,
.

, in situ,
, ..
. ,

,
(.19),
. , -

. RLi
RMgX, , ,

SE- - ,

, .

;
.

20.4.1.

1560

1561

-,

. ,
R-M ,
, - RH. , -

.
-
: R-H,
,
. ,
, , , ,
,
: , , , .. .
-, -, -
-, N-, SH-, P-, , , - .
.

(.. "")
:
CH3MgBr + R-H CH4 + RMgBr

(20.4)

(20.4) , .,
:
RCCH + CH3MgBr RCCMgBr + CH4
C6F5H + CH3MgBr C6F5MgBr + CH4
,

, , .. (. . 19),

:

1561

1562

(CH3)3N CH2 + PhH + LiCl

(CH3)3N CH3 + PhLi

Cl
Ph3P
X

Ph3P

CH3 + PhLi

CH2 + PhH + LiX

RLi + h3 RH + Ph3CLi
. :
R = PhH2 > H2=CHCH2 > C4H9 > C6H6 > 2=CH > 3

, ,
RH (. . . 3).

20.4.1.. SE2

, ,
R-M.
,

( ) ,

()

,
(II)

IV)

--

HCl
V, .
,
.

H3

L
Pt Cl
II

(IV)

+ HCl

CH3

(L = Et3P)

H L
Pt Cl

II

L Cl
(V)

II

CH4 + L2PtCl2

1562

1563

(, Os, Nb);
. 27. ,
SE-
.

SE- ,

,
, , ,
. , ..
SE1 SE1(N) . ,
RHgR- R R - ,
,

, , , RHgR
SE2
,
.

() ():
()

RHgR' + HOAc

AcOH
()

RH + R'HgOAc
k

(20.5)

k'

R'H + RHgOAc

RH RH Hg(QAc)2
, . ( ,
R2Hg , RHgX
). (k k1) () ()
R R ,
R R Me, Et, i-r, tBu .
D
k/kD = 9-11 ( RHgR),

1563

1564

(. 3, 3.5.2). , ,
,
,

SE2-.
R
+

Hg

OAc

(VI)

R'
HgR,
RHgR rpynn R (, R=CH3) R. ,
R Me t-Bu
HgR: R' = Me < Et < i-r < t-Bu.
,
, VI;
c R' HgR .
(R) (
20.3) , HgR' , R
"" , , : R
= Et > i- > Me > t-Bu.
. (1) Et i-

t-Bu, ,
-g VI. (2) ,
Me Et ( Me i-)
,
.
.
. , Men Et(4-n)b (
=0,1,2,3,4) e -b 8,6
Et-b,
e Me-Hg 2
Et-Hg. ,

1564

1565

, .
, ""
R RM , ,
- t-BuM
S2 ( S2(N) ), ''"
VI

20.4.1.. SEi

9,33 ,
10,88 , .. . ,
-g
, , - -g (3)2g
, CH3HgCl.
( RHgI
).
S2-
(, ) - -g,

R2Hg

RHgX

, . ,
,
,
R2Hg.
, ,

, ,
, , Nu- (RHgRNu)-
(RHgRNu2)2-;

1565

1566

4. ,
, . ,
NaI (PhHgBrI)-,
-,
, , .
-g
R?Hd RHgX ,

SE2 SE2(N) SEi . ,
SE2 ( VI),
(
).

CH3

CH3HgI + AcOH

Hg

OAc

I
(SEi)

CH4 + HgIOAc
CH3HgI (9,25 )
, ,

CH3HgIH+,

SEi, .
(. 3, 3.3.6.)
(..
).
,
.
, , ,
, , F- (. 3.2). R RHgX
, , R=CF3 p-NO2C6H4CH(CO2Et),
,
, SEi - , ,

1566

1567

, C-Hg.
: e,
? ,
.
R RHgX
.
SEi-
RHgX,
. , RHg (R = -Bu, -Bu,
, [PhCMeCH2]) . ,
, HClO4
100 ,
R2Hg, lO4. "" ( HClO4)
CH3COOH2+, SE2 -.
lO4 CH3COOH2+,
, e
( CH3COONa,
), SEi, -, a :
R

Hg

H
O

R Hg
H

H
C

R
O
CH3

CH3
(SE2)

(SEi)

: R =

-Bu > .- > > ,

(. ).

SEI
. .
, (

1567

1568

, CH3OCH2CH2OCH2CH2OCH3) HCl r,
:
(C2H5)3B + RCOOH (C2H5)2BOCOR + C2H6

.

.

Et3B

Et3B + RCOOH

Et

O
C R
HO

Et
Et

Et
B

O
C

Et
H

Et
B O
C

,
- VII.

+ CH3COOD

D
H

()

S -20 - - 30 /(.),
- (. . .
3) . SEi SE2
,
.
20.4.1. SE1(N)

S2 SEi.

1568

1569

Sl ,
, () . ,
,
RM. SEl , e R R-. SEl -

, (Zn, Cd, Mg,

Al ..) , , . ,
-
R2Zn + H2N

CH3

RZnNH

CH3 + RH

,
R: Et > i-r > -Pr ~ Me
> -Bu. , " "
SE2 SEi -.
SEl
4- (VIII)

----

(XI).

VIII HClO4,
-.
RHgX - 1:1 1:2
(IX).
Cl-

HN

Cl-

HN

CH2HgCl

CH2HgCl2

HN

CH2HgCl32

HN

CH2

(VIII)

H+

HN

CH3

HN

CH2
(IX)

3-

(X)

e .

1569

1570

CH2HgCl

CH2

HN

HN
(X)

()

,
HgCl2 Cl-
HClO4. HgCl2
.

SE1(N), - .
XI, II (
15,7 ), (max 540 )
. u4N+Br ,
.
- :
NO2

CH COOEt + Br
HgBr

NO2

CH COOEt
HgBr2

XI ()

NO2

CH COOEt + HgBr2

XII (; )

XI ,
Bu4N+Br- --
. CH3OD ,
-, - .
II.

1570

1571

NO2

CH COOEt + Br

NO2

CH COOEt

HgBr

NO2

HgBr2

NO2

CH COOEt

CHD COOEt

D
NO2

MeOD

CH COOEt

NO2

CHD COOEt+

O
N

CH COOEt

NO 2

CHD COOEt
D

..

IV
RMR3 -x .
pea :
RMR'3 + R''O

R''OH

RH + R'3MOR''

(M = Si, Ge, Sn; R = XC6H4C=C, Ph3C,

Ph 2CH, XC6H4CH2 .;
R' = Alk Ar; R'' = H CH3)

S2-;

RC6H4CH2(CH3)2

X , , ,
, .
RH R :
R = PhCC > 9- > Ph3C > Ph2CH > CH2=CHCH2 > PhCH2

.
(1) SE1(N), e R
SN2:

1571

1572

RNR'3 + R''O

R' R'
R''O M R

R''OMR'3 + R

R'
R + R''OH

RH + R''O

(2) SEl (N) :

RMR'3 + OR''

(RMR'3OR'')

[R ...-MR'3OR'']

R + R''OMR'3

R + R''OH

RH + R''O

(3)
( = Si,
M = Sn ):
RMR'3 + OR''
(RMR'3OR'') + R''OH

(RMR'3OR'')
RH + R''OMR'3 + R''O

SEi -,
,
, .
, S1(N) ,
Si-
.
.
R-M SE1-

R-

.,

- RH.
R , ,
RM
, (,
). .20.1..
SEi-. ,
RM (RH)

1572

1573

,
. ,
( )
, e
,
.
, -
,
SEi.
(RH), .20.1..
lgk

lgk

(a)

()

pKa (RH)
.20.1.

pKa (RH)

RM (RH) Sl(N) () SEi ()

, . 20.1. . , RSiMe3 -
, R2Hg (R = 2, CF2COOMe ,
CFCICOQMe, PhCC, 6H6, CF3) -2-Bu4N+I-
, . 20.1.. ,
R2Hg

HCl

(.20.1.6) (RH) 25-27.

, ,
SE1(N) ( .
20.1.) SEi SE2 ( ) R.
SE1 .

1573

1574

20.4.1. . S'

"" S
. SN -
.
: S2 ( SEi ) SE,
, , , (SE)
, .
, HCl
, -1,
107 , -.
SE'

H3

CH3

CH2
H

HgBr

CH2

+ HgClBr

Cl

- - CH3OD
DCl -1, 3.
H3

+ DCl

CH2SnMe3

SE'

CH3

CH2

CH3OD

+ Me3SnCl

SE- . ,
F3D DCl ,
,

- - .
DCl
- -, -. -,
DCl,
- .

1574

1575

Cl

H C HgCl

Hg

H
C

Cl

D
H

+ DCl

+ HgCl2

III - ,
. DCl
- - -.
D
CH2
H

H
D

H
C

DCl

CH2D

Cl

D
-HCl

D
CH2

CH2D

Cl
D
H

-DCl

III , HgCI2
-.
, .
,
.
CH2

CH2HgCl
D

D
+ HCl

H + HgCl2

20.4.1.. -

, .
R3AuIIIL

1575

1576

(L

h3;

, ),
(. . 27), ,
-. ,
(3)3uL 20 () () ( IV).
(CH3)3AuL + HX

25 oC
C 6 H6

L = Ph3P
X = CH3COO

CH3
CH3 Au L + CH4
XIV

(HCl,
r, HI, CF3COOH, HCIO4, CF3SO3H , HNO3, n-CH3C6H4SO3H . .,
, ..
- .

() () 4 CD3H,
- - 4.
CH3
CH3 Au L

HNO3

CH4

CH3
HNO3

CH3D

CD3

CD3 Au L
CH3

()

()

, -(3)2RAuL 4 RH, - 4.
CH3
CH3 Au L
R

CF3COOH

CH4
RH

CH3
CF3COOH

R Au L
CH3

()

()

4 RH

-, : R = CH3 >> Et > -r > ir.

,
,
. - ().
1576

1577

() ()
.
-, -,
,
(CF3SO3H >> CF3COOH, l , HNO3 >> 3) .

, , Me >> Et > -r > i-r,
-u (. 20.4.1.). ,
SE2 V.
- R

-u

- .

CH3

Au

R
(XV)

H
X

- ,
, .

-
Pt(II).

20.4.2.

e ,
.
, .. , ,
:
,

F2

Cl2

Br2

I2

2,9

2,4

2,6

2,4

2 (0,4 ) O3

1577

1578

(2,0 ).

.
,
, .. .
:
,

Me2Hg

Et2Hg

i-Pr2Hg

t-Bu2Hg

9,33

8,45

8,03

7,57

MeSnMe3

EtSnMe3

i-PrSnMe3

tBuSnMe3

9,70

9,1

8,8

8,6

, , ( ),
d- (. . 27).
( ,
, - -.
, R2Hg, R4Sn, R4Pb, RHgCl, RHgBr .,
, CH3HgI
). ,
, (. 19).

,
e -

R-M + Hal2 RHal + MHal

-
RM
.

- - RM+ .

Hal- .

.
(1) SE2- SEi -
:

1578

1579

R M
Br Br

R-M + Br2

RBr + M + Br

SE2 ( )

R-M + Br2

[Br...Br...R...M]

Br + BrR + M

SE2 ( )

R M

R-M + Br2

RBr + MBr

Br Br
SEi ( )

(2)

(. 2.4.1).
(.. 27), :
Cl
R

FeII(CO)2Cp + Cl2

FeIV(CO)2Cp
Cl

R Cl + Cl

FeII(CO)2Cp

()
R = - -PhCHDCHD-,
Cp = C5H5 ( )

(3) (SET-), :
PhCH2Co(DMG)2 + ICl

[PhCH2Co(DMG)2 ICl ]

PhCH2Cl + ICo(DMG)2
DMG () = CH3

C CH3

O N N OH

, .
(4) SN2 (
) , :
Br2

2Br

Me4Sn + Br
CH3 + Br2

Me3SnBr +

CH3

CH3Br + Br ..

, , -, , ,
(. . 14) , -,

1579

1580

. , ,

- (XI),
4- 70% - 1,3 : 1.
HgBr
H3

+ Br2 + F

CH3
()

Br
CH3

Br
+ F

CH3

CH2Br

()

()

28:1. , :
( ) ( )
. ,

2.2%

,
.
, () ,
,
:
RHgBr + Br2

[RHgBr Br ]
-
()

RBr + HgBr2 ()

[RHgBr Br ]
()

R + Br2

R + HgBr2 + Br ()
RBr + Br ( ..)

- ()
( , . . 14) ()
.
.
, -
, (1), (2) (3),
1580

1581

. ,
, , ,

. , ,

. ,
-

.
,
SET-,

, . . 9 ( 9.2.4)
.
SET-
, SE- -
,
,
.

,

.
- .

20.4.2..

RHgBr + Br2

MeOH

RBr + HgBr2

""
, ..
R = t-Bu > i-Pr > Et >Me
1581

1582

-g (. ).
, , SE2
(SEi), SET-..
R HgBr

R Hg + Br2

RBr + HgBr2 (SE2)

Br Br

R HgBr + Br2

(RHgBr Br )

(R HgBr2 Br )

RBr + HgBr2

(SET)

R-Sn

RSnMe3

, .
:
R = Me > Et > i-Pr > t-Bu

Sn-R .

"" :
R = t-Bu > Me > Et > i-Pr
-,

. ,
- ,
R-Sn r2
.
, ,
, ,

, , R4Sn.Br2.
, ,
, ;
,
-

1582

1583

.
-, -
CCl4,

,
.
, -,
:
RnM + I2

[RnM.I2]

[RnM I2 ]

RI + Rn-1MI
(M = Pb, Sn, Hg; R = Alk; n = 4 2)

,
(VI) : -
(VIIa) (XI).
R
RnM

X2

:X2

R(n-1)M
()

XVI

()

,
, M, R 2.
XI ,
;
R3SnBr.r2 VI,
:
R'3SnBr.Br2

R'3SnBr + Br2
R3Sn
R

R3Sn

Br
Br

Br

Sn R'3

Br
SnR'3

R
Br

Br

VI
R3SnBr,
: R4Sn .

1583

1584

= k3 [R4Sn][Br2]2
SEi SET - .
Br

Br

R3Sn

Br

(SEi)

Br Br

Br
R

Br

Br

R3Sn
Br

Br

R3Sn

Br

R
R3Sn

Br

Br

Br

R3Sn

Br

Br
Br Br

Br Br

(SET)

, RSnMe3
Sn-R
R,
" " R = t-Bu > Me > Et > i-r.
, ..

. ,
VI . ,
,
,

Sn-R,

,
.
,
. RSnMe3
" " Me > Et > i-r > t-Bu .

1584

1585

Br-Br ... HOMe

R
R3Sn

R-Br

(SE2)

Br ... HOMe

R3Sn-OMe
H

:OMe
H
R Br Br ... HOMe

(SET)

R3Sn-OMe
H

SET-,

" ".

. ,
rONO2.2Py
20% PhCH2Br, 36% PhCH2ONO2 13%
.
-
VII.
Ph

CH2
Hg

PhCH2 + HgBrCl + NO3

Br

ONO2
ONO2

Cl

Br
Cl

PhCH2Br

PhCH2ONO2

XVII

PhCH2Cl

,

, SET- SE-
.

20.4.2..

,
.

1585

1586

- ,
SnR3,
. S2 -
(. 20.2.2), SET-, -, ,

. ,
, , ,
SnR3 (. 20.1).
20.1.

--Sn

C2H5

CH3 C* Sn
H

+ Br2

C2H5

MeOH, Br

CH3 C* Br + Br Sn
H

-BuSn(i-Pr)3

45%

(-Bu)3Sn

35%

-BuSn(CHEt2)3

8%

-BuSn(-C5H11)3

28%

* : "45% " , 45%, ..

72,5% 27,5%
. "28% " ..

SnR3
, .
H
Et
Me
H C Sn
Et

Me
C Sn
Br2

Me
H C Br
Et

()

+ Br2
H
Br2

Me
C Sn
Et

Br

Et
()

( )

1586

Me
C H

1587

SnR3
, R =
.

-e
(1), (2) (3), .
, ,
, ,
. , , ,
, , .
, , , ,
.
, .

Li + X2 25 oC

t-Bu

Br

H + t-Bu

t-Bu

-4-H -

Br
-

X2 = Cl2 : = 71:29
62:38 ()
Br2
75:25
I2
()
N.Br
26:74
2

C B

OMe
Br2
C B R
Na R

R MeONa
R
Br

Ph
H

Mn(CO)4PEt3

Br ...Br

OMe
R
B
R

+ R2BOMe + NaBr

H + X2

Ph
H

()
X 2 = Cl 2 % :
Br 2
I 2

1587

81
67
32

Ph
+

D
X

()

1588

(CH2=CH)4Sn + 4PhLi

4CH2=CHLi + Ph4Sn

RR'NCH2SnBu3 + BuLi

RR'NCH2Li + Bu4Sn

.

(.., .),

() .
= =g
-, -, -

.
RHgX + Hg*X2

RHg*X + HgX2

( )

R2Hg + HgX2
RHgX + R'Hg*X

2RHgX
RHg*X + R'HgX

( )

R2Hg + R'HgX

RHgR' + RHgX

( )

R2Hg + R'2Hg

2RHgR'

( )

. (..
, ),
203Hg.

:
RHgX + 203HgX2

EtOH

R203HgX + HgX2

R = CH3;
X = Br, I, NO2, OAc
R = -Bu; X = OAc, NO2

,
:

= k2 [RHgX] [HgX2]

1588

1589

, e

-uHgOAc, ,
- . ,
, S2 SEi
:
X
R

HgX

Hg

HgX

Hg

SEi

SE2

LiBr RHgBr +

203

gr

. , , -,

SEi

-,

.
LiBr
,
.
Br

Br
R

Br

Br
Hg

Hg
Br

Hg

Hg
R

Br

Br

Br

Br

,
HgII,
:

I > Br > Cl > OAc

( R)
, , ,

-,

.
gr2 -

1589

1590

Br

HgBr2

Br

HgBr3

HgBr42

. , LiBr ,
, e
, R-Hg.
SEi .

--

(V) 203HgBr2.
X

CH COOEt + 203HgBr2

CH COOEt + HgBr2
203 HgBr

HgBr
XVIII

80%- , , , ,

.

. , V
HgBr2 10% ,
.
SE1(N)-a.
X

CH COOEt

HgBr

Me2S

CH COOEt
O:

CH COOEt

Me2S
203

HgBr2

O:
X

HgBr
CH COOEt
203

HgBr

HgBr

SE1-:

= NO2 > I > > t-Bu

, , ,
SE1-.
SEi- ,

203

HgBr2 V

SE2 - , e 1590

1591

g. SE1(N)
: ,
. SE1
, ,
,

. ,
SE1 (. . 20.5), SE2.

V, ,
, , ..
= NO2 > I > > t-Bu
SEi,
.
H3N:
2X

CH COOEt +

203HgBr2

:NH3

Hg

NH3

Br

C
Hg

CHCl3

HgBr

Br

C
COOEt COOEt
X

X + HgBr2.(NH3)2

CH Hg CH

,
,
, - X. ,
,

-g

SEi-

X,
:

1591

1592

CH COOEt + CH3

Br

203

HgBr

HgBr

Br

H3N:

NH3
CHCl3

COOEt COOEt

:NH3
Br

203Hg

Br

CH COOEt

CH Hg CH

CH3

Br

C
Hg

+ 203HgBr2.(NH3)2

CH3
, ,
R2Hg (II), SEi ,
:
HgCl
CH3
Hg CH2 C
OMe

Ph

OMe

+ PhCMe2CH2- 203HgCl
52%

203HgCl2

CH3

203HgCl

OMe

+ PhCMe2CH2-HgCl
48%

()

CH3

CH3

CH3
H C* HgBr + BrHg C H
C2H5
C2H5

CH3
H C* Hg C H + HgBr2
C2H5
C2H5

()

gX2, RHgX, R2Hg

X .

SEi SE2.

1592

1593

, .. ,
R, , - (
R) *g.
:
(1) R X.
R Hg

R
X

RHgX + R *Hg Ro
*Hg
Ro

(2) R Ro.
R Hg

Ro

RHgRo + R *Hg X
*Hg

(3) g *g.
Hg

Ro

R Ro X R
*Hg

Hg
X

R
*Hg

(4) .
(5) , .
2X *Hg Ro

Ro2*Hg + *HgX2

R2Hg + *HgX2

2R*HgX

(1)
, .. V(*Hg) = V(Ro).
(2) R2Hg RHgX
, .. V(*Hg) = 0. (3) V(Ro) = 0.
(4)
R . (5)
V(R) >
V(*Hg). , V(Ro) = V(*Hg).

1593

1594

,
, .. (1).
,
,

LiClO4 > LiBr >LiNO3 > LiOAc

, ,
. , pea
SE2 .
. , ,
(CH3)2Hg (CD3)2Hg 65
D3g3. Hg-Hg
XIX.
H3C
Hg

CH3

CD3

CH3 Hg

Hg CD3

(XIX)

CH3

CH3

Hg CD3

H3C Hg

CD3

H3C Hg

Hg CD3

CD3
+

CH3
Hg CD3

CD3

R2Hg + R'2Hg

RHgR'

,
R- R-, :
R ...................

Me

Et

Et

-Pr

R ..................

Et

Ph

CH=CH2

-C3F7

1,8

5,0

15

> 2.103

20.4.3..

(. 20.4.1.),
-
. ,
XX --,
1594

1595

, ,
HgCl2,
a -:
= k3 [ArCH2B(OR)2] [HgCl2] [OH-]

XX -.
O
ArCH2

O
ArCH2 B
OH O

+ OH
O

CH2OH

CH2OH
O

CH2OH

HgCl2

ArCH2HgCl + HO

ArCH2

B O
Hg
Cl
Cl

+ Cl
O

CH2OH

.
Ph
CH3

B(OR)2

Ph

HgCl2

CH3

C HgCl

()

. , - -[Me3CCHDCH]3B
- 3DD HgQAc, .. .

g2:

MgBr
()

+ HgBr2

HgBr
H

1595

1596

H
()

+ HgBr2

H
HgBr

MgBr

S2. :
Hg(OAc)2 > HgCl2 > HgI2 >>HgI3-

HgI3- ,
Sn-X.

RSnR'3 + HgX2

SnR'3

RHgX + R'3SnX

HgX2

R4Sn ,

:
R = Me >>Et > -Pr ~ -Bu > i-Bu >> i-Pr
, -

2+

RCo(DMG)2, DMG- - , Hg
R Co(DMG)2 + Hg2

H2O

CH3Hg + Co(DMG)2

:
= k2 [R-Co][Hg2+]
R e :
R = > Et ~ -r ~ i-Bu >> i-Pr

- Me3CCHDCHD-Co(DMG)2 Hg2+
lO4 - Me3CCHDCHDHg+, ..
. , SE2 .

1596

1597

C Co + Hg2

Hg

Hg

C Co

+ Co

[Co = Co(DMG)2]

a F()2R
, R
, , , , . R = -CHDCHDPh -CHDCHDBu-t
RHgCl .
,
RHgCl F()2l, x RCl
CpFe(CO)2HgCl.
RCl, HgCl2.
()

OC Fe
CO R

+ HgCl2

FeCl + RHgCl

()

FeHgCl + RCl

()

RCl, CO, HgCl2 ..

Fe = CpFe(CO)2

R = t-
:
= k3 [RFe][HgCl2]2
R = i-r ( gCl2).
,
, -.

OC Fe
CO R

k1

+ HgCl2

+ HgCl2

OC Fe CO
R HgCl
k2

HgCl3
OC Fe CO
R HgCl

OC Fe CO
R HgCl2

1597

1598

()

HgCl3
OC Fe CO
R HgCl

OC Fe
CO Cl

+ RHgCl + HgCl2

+ RCl + HgCl2
()

OC Fe
HgCl
CO

()

HgCl

OC Fe CO
R HgCl2

OC Fe CO
R HgCl2

, RHgCl
(). o,

R-Fe,

R+,

() -

(+)-h(3)F()2
PhCHClCH3, . ()

,
R-Fe , R+, .. R = i-r

-511.
, ,
.

1598

1599

20.5.
-
,
-, .. .
20.1,
S1
. ,
.
, ,

-.

.
,
. :
C: + C O

C C O

,
.
, .

..

(.. 17).
R'
C C

OH

R'

R + B

-HB

C R' +

C C R
O

R'

C C

HB

H C C R

-B

CN
R

C R + B
OH

CN
+

-HB

C R
O

1599

C R + CN
O

1600

, .. ,
:
R Na
R'

C O

Na

R'

HA

C O

RH

R''

R''

, -

-, .. , R =
, .
. S- (. 20.2.2).

,
( ).
, - ( NH2-)
,
SE1
OH
R

C R' + OH

R + R'COOH

R'

RH + R'COO

.
- - (.
. 17)
R
R'OOC

C C

R + OH

R OH
R'OOC

C C R
R O

R O
R
R'OOC

+ RCOOH

R'OOCCH2R2 + RCOO

R
EtO-,
.

(. 17).
, :

1600

1601

HO

HO

CH3

CH3

CH3
O

CH3
O

CH3 + OH
O

CH3

(CH3)2CH C CH2CH2CH2COO
O
(CI2, r2 I ,
F2) ):
CH3

Br2

C R

CHBr3 + RCOO

OH

, :
OH
Br3C

Br3C

C R + OH

C R

Br3C

+ RCOOH

O
CHBr3 + RCOO

F2 , CF3COAlk
CF3COOAr F3.

,
. t-BuOK-H2O (10:3) ,
t-BuOK
.
:
Cl
ArH +
COCl

Cl
Ar

t-BuOK-H2O

ArCOO

+ PhCl

pa- .
ArCOCR3,
R3CNH2, .

1601

1602

-CRRR.

, :
NH K

NH2
Ar

C CR3

Ar

C CR3 + KNH2

O K

-NH3

Ar

Ar K

C CR3

C CR3
O K

NH K

NH K
Ar

KNH2

HA

C CR3
O

K O
O
ArH + R3C

C
NH2

. , , COR, R2C=CH, NO2, X3C ..
,
.
.
,
, -:
R

C
O

CH2
H

C O

R C

CH2

OH

C O
O

SE-. e
, ,
2, SE-.
O
R

C O

R + CO2

HA

RH + CO2

(SE1)

,
R ,
,
R-.

1602

1603

(. 20.2.2), :
CN

CN
Et C* CO2 M

Et

+ ROH

H OR
C O M

Ph O

Ph
CN
Et

C:
Ph

CN

H OR

(c)

Et C* H

Ph

CO2

, ,.
2
,
( 20.2.2) .
,

---

(XXI)

.
O CH3
Ph

C* C

O C6H13

O CH3

HB

Ph

-CO2

S C* H
O C6H13

B
DB

O CH3
Ph

O C6H13
(c)

(c)

XXI

S C* D

Ar

S
O

RO

R O

ArN

S
O

1603

Ar

P
O

1604

21

21.1. ................................................................................................................ 1605

21.2. ............................................................................................................................ 1607
21.3. ..................................................................... 1609
21.4. .................................................................................................. 1613
21.5. ..................................................................................................... 1618
21.5.1. .............................................................. 1618
21.5.2. . ................... 1620
21.5.3. ............................................................................................ 1621
21.5.4. ............................................................................................... 1623
21.5.5. ................................................................................................ 1623
21.5.6. . " "
.................................................................................................................................. 1624
21.5.7. ............................................................................................. 1627
21.5.8. ............................................................................ 1627
21.5.9. . ,
................................................................................................................... 1629

21.6. .......................................................................... 1629

21.6.1. ................................................................................................ 1630
21.6.2. . ................................................ 1630
21.6.3.
. , ................................................................. 1631
21.6.4. . .............. 1631
21.6.5. ...................................................... 1636
21.6.6. ............................................................................................. 1638
21.6.7. ......................................................................................................... 1638
21.6.8.
.................................................................................................... 1640

21.7. 1644
21.7.1. ............................................................................................................ 1644
21.7.2 . ..................................................................................................................... 1645
21.7.3. ............................................................................................................... 1646
21.7.4. ............................................................................................................ 1647
21.7.5. .............................................................................................................. 1648

21.8. .......................................................................... 1649

,
,
,
.
, ,
RNH2, R2NH R3N.
,
. ,

1604

1605

,
.
CH3CH2CH2NH2; (CH3)2CHNH2; (CH3)3CNH2

(CH3CH2CH2)2NH; (CH3)2CH-NH-CH2CH3; ()-N-2

(CH3)3N; 6H11N(CH3)2; ()-N(CH3)2

R4N+X-
,

(C4H9)4N+Br-; C16H33N+(CH3)3Br-; C6H5CH2N+(C2H5)3Cl-; (C8H17)3N+CH3Cl-

21.1.

.
.
(CH3CH2CH2)3N

(CH3)2NH

--

NH2

CH3
[(CH3)2CH]2NH

CH2CH3

(IUPAC)
- NH2 -.
CH3-CH-CH3

CH3CH2CH2NH2
1-

NH2

2-

CH3 NH2
CH3-CH-CH-CH2-NH2
3--4-

,
.

1605

1606

CH3
CH3CH2CH2N(CH3)2

(CH3)2CHCH2CH-N(CH2CH3)2

1-N,N-

2-()-4-

CH3
FCH2CH2-CH-NHCH2CH3
3-()-1-

CH3
CH3CH2-CH-N

CH3
CH3CH2CH-CH2CH2-NH

CH3

CH3

CH2CH3

1-()-3-

2-()

Chemical Abstracts ,
,
, .
, .
"".
H3(CH2)3NH2

CH3CH2CH2CHCH2CH2NH2

(CH3)2CHNH2

CH3
1-

3--1-

CH3CHCH2NH2

2-

CH3-CH-CH=CH-CH3

CH3
2--1-

CH3CHCH2CH3

NH2

NH2

3--2-

2-

,
, , .
N-.
(H3)2NCH2CH2CH3
N,N--1-

(CH3CH2CH2)2NH

CH3CH2CH2NHCH2CH(CH3)2

N--1-

2--N--1-

(CH3CH2CH2)2NCH2CH3

CH3CH2CH2NHCH3

N--N--1-

N--1-

, Chemical Abstracts,
.
.

1606

1607

Br
N(CH2CH3)2 CH3
N,N-

NH2

NH2

4-

3-

. , -,
Chemical Abstracts.

21.2.
, , . N-
1,008 , H-N-H 107,3 .
sp3-
sp3- . ,
.
o
1,008 A

H
107,3 o

o
1,474 A

CH3
113 o

N
H

o
1,47 A

CH3

105,9 o

N
CH3

CH3
108 o

N-H 1,011 , C-N 1,474 .

H-N-H H-N-C 105,9 112,9 .
H-N-H .
C-N 1,47 , C-N-C 108.
- ,
, ,
.
N
C6H5

N
CH3

CH3

C6H5

,
(. 8).

1607

1608

, ,
.
, 5-6
/, 102 - 103 20.
sp2-
, Z - .

N
C6H5

C6H5

CH3

C6H5

CH3
H

H
N

CH3

.
(I).
N CH2
CH2
CH3

CH3

CH2 N

. ,
.
,
20-25 / ,
C-N-C
, ,
120.

, 8-9 /.
.
,
,

. ,
-
20-25 /.

1608

1609

0-20 .
II III ( ),
25 /.
Ph
Ph

N
Cl

CH3
CH3

II

N
OCH3
III

,
.

NF3 60 /.
RN(OR)2
22-25 /. ,
N(OR)3 ,
.

.
, :
CH3
N
C6H5CH2

CH3
I

N
C6H5

C6H5

CH2CH=CH2

I
CH2C6H5

CH2=CHCH2

(S)

(R)

21.3.
a .
, :

1609

1610

CH3
HO
HO

CH3

CH3
HO

CHCH2NH

HO

CHCH2NH2

CH2CHNH2

H
N

HO

CH3

()

CH2CH2NH2
N
CH2CH2NH2

NH

Cl

CH2CH2NH2

CH3O

CH3

CHCH2CH2N(CH3)2

OCH3

OCH3

NHCH3

S
N

Cl

Cl

CH2CH2CH2N(CH3)2

CH=CH2
HO CH

R1O
O

CH3O
N

R2O

H
H

N CH3

R1=R2=

R2=H; R1=CH3
R1=R2=C(O)-CH3

1610

1611

H5C6

O C

H3C
N

H5C6

O
CH2CH3

CH2CH3
N

CH

CH

CH2CH2C6H5

N
(C2H5)2NCH2CH2O C

CH3 O
C

OCH3

NH2

C
O

CH3
H2OH
CH2OH

HO
CH3

CH2CH2OH
N

N
CH3

( 6)

S Cl

NH2

( 1)

COOH
N

.
( ""
) .
,

, .
, .
.
. ,
, ,

() ,

1611

1612

,
. , , 2

6522NH2.

- 2-.

.
.
. .
. ,
,
. - ,
.
, .
, ,
,
- .
.
, 300 .
.
., ( 1) . -
.
, .

.
, ,
, .
.
, .

.
, . ,

1612

1613

, .
,

O
(CH3)3N-CH2CH2OC

CH3

+ H2O

(CH3)3N-CH2CH2OH + CH3OOH

. ,

21.4.
,
.
,
.
,
, .
, ,

ROH + H

ROH2

RNH2 + H

RNH3

, ,
. -
KB
.
RNH2 + HOH

KB

1613

RNH3 + OH

1614

[ RNH ][OH ]
[RNH ]
+

KB =

, KB,

) .

KB

Ka,

(.. 3)
Ka

RNH3 + HOH

RNH2 + H3O

[ RNH ][ H O ] ; pK + pK = 14
=
B
a
[ RNH ]
+

Ka

pKa ,
, . 21.1.
pKB ,
, .. , .
: R2NH > RNH2 ~ R3N,
+I- ,

.
.

: R3N > RNH2 > R2NH > R3N (. 3).

. ,
N-H . a 35,
a ~40. ,
, .
,
() .
- .
[(CH3)2CH]2NH + -C4H9Li

pKa~40

1614

[(CH3)2CH]2N-Li+ + C4H10
pKa~50

1615

,
,

.
CH3

CH3
N Li
CH3

[(CH3)3Si]2N Li ,
CH3

-:
10-11
.

.
9,37, C6H5NH3+ (a = 4,63)
, .
+

C6H5NH3 + HOH

Ka

C6H5NH2 + H3O

Ka = 2,5 . 10-5 M; pKa = 4,63

CH3NH3+ + HOH

Ka

CH3NH2 + H3O+

Ka = 2,7 . 10-11; pKa = 10,62

21.1

25

pKa (25 oC)

pKa (25 oC)

NH3

9,24

(CH3)2NH

10,73

CH3NH2

10,62

(CH3CH2)2NH

10,85

CH3CH2NH2

10,64

[(CH3)2CH]2NH

11,13

CH3CH2CH2NH2

10,54

CH3CH2CH2CH2NH2

10,63

(CH3)3CNH2

10,60

(3)3N

9,80

-C6H11NH2

10,68

(32)2N

10,75

C6H5CH2NH2

9,33

NH

11,31

11,12
NH

10,38
N CH3

1615

1616
CH2=CHCH2NH2

9,49

H2N(CH2)6NH2

11,10

C5H5N ()

5,23

H2NCH2CH2NH2

9,92

C9H7N

4,90

H2NCH2CH2CH2NH2

10,55

10,46

N CH3

: - I +
. ( = 4,31)
, ( = 4,74)
-I .
.

.

, () :
+

NH2

NH2

,
" " - - ,
/-
.

, -,
- .
s-,
. ,
t
-, , s. . HNH (113,9) ,

1616

1617

(107,3) . N
39,4:

H
H

(. 21.2.)
21.2

a 25
(25 )
-

CH3-

4,44

4,72

5,10

OCH3-

4,52

4,23

5,34

F-

3,20

3,57

4,65

Cl-

2,65

3,52

3,98

r-

2,53

3,58

3,86

I-

2,60

3,60

3,78

CN-

0,80

2,75

1.74

CF3-

3,50

2,45

NO2-

-0,26

2,47

1,02

CF3SO2-

1,80

-0,01

N- N,N-, ,
, . 55N(3)2 a = 5,07,
55N(25)2 a = 6,57. (
) 0,1 pa , 4-
50%- , 2,4- ( = -4,4)
(. . 3).
, , ,
.

1617

1618

.
, ,
.

21.5.
.
.

,
.

21.5.1.

. . 1849
,

,
.
, ,
.
,
, .
,
,
, ,
.
+

RNH3 Br + NH3
RNH2 + RBr

RNH3 Br

RBr + NH3

RNH2 + NH4 Br
R2NH2+Br-

1618

(2)
(3)

1619

R2NH2+Br- + NH3

RNH2 + NH4+BrR3NH+Br-

R2NH + RBr
R3NH+Br- + NH3

(5)

R3N + NH4+BrR4N+Br-

R3N + RBr

(4)

(6)
(7)

, ,
.
.
, ,
,
. ,
.

(1)-(7).
. e
,

.
.
1-
20 , 45% , 43%
.
,
.
CH3(CH2)6Br + NH3
1M

3M

C2H5OH
25 oC

CH3(CH2)6CH2NH2 +
45%

+ [CH3(CH2)6CH2]2NH + [CH3(CH2)6CH2]3N
1%

43%

,
, .

1619

1620

21.5.2. .

1887
.
N-
.
O

O
C

NK + RX 80-100 oC
C

NR + KX
C
O

N-
:
O

O
C

C
NR + NH2NH2.H2O
C

C2H5OH

NH
NH

+ RNH2

.
.

300-350. N-H
~ 8,3. -
- .

-.
O

O
C
NK + BrCH(COOC2H5)2
C

80 oC

C
NCH(COOC2H5)2
C
O

1620

1621

O
C
C

O
C

1) C H ONa, C H OH
NCH(COOC2H5)2 2) C2H5CH Br 2 5
6 5
2

NC(COOC2H5)2
C

NH3

H2O

CH2C6H5

64%

C6H5CH2CHCOO

H , to

O
C

CH =CHCOOC2H5
NCH(COOC2H5)2 C H2 OK, C H OH
2 5
2 5

NC(COOC2H5)2
C

HOOCCH2CH2CHCOO
NH3

H , to
H2O

CH2CH2COOC2H5

75%

-
.
O
C

O
C

H2CH2Br
+

NK

C
O

HO

HO

H2CH2-N

80 oC

OH

OH
O
C

H2CH2NH2
+

NH2NH2 H2O
C2H5OH

HO

NH
NH
O

OH

21.5.3.

,
( 18).

1621

1622
H2

RC N

RCH2NH2

Ni
LiAlH4

CH3CH2CH2CH2CN

CH3CH2CH2CH2CH2NH2

CN

91%

CH2NH2

LiAlH4

88%

CH3

CH3

, , ..
-50
- ( -78) , (. 18).

.
C6H5CH2CN + H2

Ni
140 oC

C6H5CH2CH2NH2 + C6H5CH2CH2NHCH2CH2C6H5
70%

20%

:
RCN + H2

RCH=NH

RCH=NH + H2

(1)

RCH2NH2

RCH=NH + RCH2NH2

(2)

RCH=NCH2R + NH3

RCH=NCH2R + H2

RCH2NCH2R

(3)
(4)

, ,
,
, (3) .
NC(CH2)8CN + H2

Ni, NH3, C2H5OH

100 ., 125 oC

H2N(CH2)10NH2 (80%)

, ,
.
, .
,
.
C6H5CH2CN + H2

Ni,
(CH3CO)2O

1622

C6H5CH2CH2NH-C
(97%)

O
CH3

1623

:
OH
O + HCN

OH

LiAlH4

CH2NH2

CN
H3PO4
t oC

CH2NH2

Ni, H2

CH2NH2

21.5.4.

(. 18),
.
O
C-N(CH3)2
CH3O
CH3O

LiAlH4
, 36 o C

CH2N(CH3)2
(88%)

CH3O

O
CH2CNH2

LiAlH4
, 36 o C

CH3O

CH2CHNH2

CH3O

CH3O
H3(CH2)10C

O
NHCH3

LiAlH4

(40%)

CH3(CH2)10CH2NHCH3

.
(CH3)3CCNH2
O
CH3(CH2)4CN(CH3)2
O

B2H6
, 65 o C
B2H6
, 0 o C

(CH3)3CCH2NH2
(79%)

CH3(CH2)4CH2N(CH3)2
(95%)

21.5.5.

1623

1624

Pd/BaSO4.
- (. 22).
6H5CH2CH2Br + NaN3

C2H5OH

C6H5CH2CH2-N=N =N

(86%)

C6H5CH2CH2-N=N+=N- + LiAlH4

C6H5CH2CH2NH2
(89%)

Br

N3

NaN3, 30 o C
18--6
CH3CN

CH2CH2CH2Br

NH2

LiAlH4

(CH2)3N3

NaN3

(54%)

(CH2)3NH2

LiAlH4

C2H5OH

(89%)

21.5.6. . "
"

, ,

.
,
.
" " :
R1C R2 + NH3

-H2O

H
R1

NH

C6H5-C-H + NH3

R1C R2

H2/Ni

-H2O

C6H5-C-H
NH

NH2
R2

H2/Ni
90 ., 70oC

C6H5CH2NH2
(89%)

,
1624

1625

. () .
C6H5CH2-C-CH3
O

NH3

C6H5CH2-CH-CH3

H2/Ni

NH2

()

,
, , .

,
.
C6H5CH2NH2 + C6H5CHO
H2/Ni

[C6H5CH=NCH2C6H5]

C6H5CH2NHCH2C6H5

, , .
. ,
,
.
O

CH3

Pt, H2

CH3CCH3 + NH2CH2CH2OH

C2H5OH

HOCH2NHCHCH3

NaBH3CN.

N4. ,
2-3.
, -.
, N3N

.
.
O + NH3

-H2O

NH

1625

NaBH3CN
pH = 2-3
C2H5OH

H
(61%)

NH2

1626
pH = 2-3

O + NH(CH3)2 + NaBH3CN

N(CH3)2

C2H5OH

pH = 2-3

CH3C(CH2)3CH3 + NH3 + NaBH3CN

C2H5OH

(85%)

NH2
CH3CH(CH2)3CH3 (78%)

N4 .

-,

,
.
,
.
(CH3)3CNH2 + H-C

NH + H-C

O
H
O
H

+ H-C

+ H-C

100 oC

O
OH

(CH3)3C-N(CH3)2 + CO2
(85%)

120 oC

O
OH

NCH3 + CO2
(83%)

-
, - -:
R2NH + H-C

R2NCH2OH

H+

R2NCH2OH2

R2N=CH2 + H-C

R2NCH2OH

R2N=CH2 + H2O
R2NCH3 + CO2

(1885 ).
180-200 .
- -.
,
-,

1626

1627

,
.
100 oC

C6H5CCH3 + HCOONH4

C H CHCH3
, 9 6 5

(66%)

NH2
O

NH2

200 oC

+ HCON(CH3)2

(75%)

21.5.7.

, (.16).

CHNH2 2N2 .
H

1) LiAlH4,

NOH

(80%)

2) H3O+

NH2
H

1) NaBH3CN, CH3OH

NOH

(81%)

2) CH3COOH

NH2

21.5.8.

,
(. 13).

, ,
, .
1627

1628

. 22 ,
.
CH3

CH3
NO2

NH2

Fe + HCl

(74%)

C2H5OH

NH2

NO2

NH2

NO2
SnCl2

(57%)

HCl

CHO

CHO

.
NH2

NO2
NaSH

(79-85%)

CH3OH

NH2

NO2
H2N

NO2

Na2S, NaSH

H2N

C2H5OH

(52-58%)

H2N

NO2

NH2

.
- (II)
.
HOCH2 C NO2
CH3
CH3
CH3(CH2)5CHCH3
Br

NaNO2

Fe; FeSO4
H2O-H2SO4

HOCH2 C NH2
CH3
CH3

CH3(CH2)5CHCH3
NO2

Fe; FeSO4
H2O-H2SO4

CH3(CH2)5CHCH3
(90%)

NH2

,
,
.

1628

1629

21.5.9. .
,

.
18 . 26. ,

- ,
.
NaOH, Cl2
H2O, 0-20 oC

C6H5CH2-C(CH3)2-CONH2

C6H5CH2C(CH3)2NH2

,
(tranylcypromine):
1) NaN3; t o
2) H2O

COCl
C6H5

NH2

C6H5

:
CH3(CH2)16COOH

HN3; 40 oC
C6H6; H2SO4

CH3(CH2)16NH2 (96%)

,
,

21.6.

.

: sp3- sp2- ,
oe, (III) .

1629

1630

.
.

21.6.1.

, ,
, .

, sp3- .
.
(-C4H9)3N: + CH3CH2CH2CH2Br

60 oC

(CH3CH2)3N: + C6H5CH2Cl

60 oC

(CH3CH2CH2CH2)4N Br (95%)
(87%)

C6H5CH2N(CH2CH3)3 Cl

: , , , .

. c
-
.
R4N Cl

+ AgOH

-
0-20

R4H OH

+ AgCl

21.6.2. .

,
.

sp2- ,
18.
C6H5C

O
Cl

+ 2(CH3)2NH

(CH3CH)2O + C6H5NH2

CH2Cl2
0

0-20

1630

C6H5CON(CH3)2 (92%)

CH3CONHC6H5 + CH3COOH
(98%)

1631

NCCH2COOCH2CH3 + CH3NH2

H2O

NCCH2CHNHCH3 + CH3CH2OH
(88%)

21.6.3.
. ,

(. 16).
C6H13CHO + C6H5NH2

O + HN

CH3COOH

C 6H13CH=NC6H5 + H2O

C2H5OH

(82%)

n-CH3C6H4SO3H

, 110

+ H2O

(75%)

21.6.4. .

.
O
ArSO2Cl + RNH2

ArS-NHR
O
O

ArSO2Cl + R2NH

ArS-NR2
O

, .
1890
.
65S2l -

1631

1632

. 10-15
. ,
- .
N ,
"" ,
.
N- .
O
C6H5SO2Cl + RNH2

NaOH

C6H5S-N

H2O

C6H5S-NR Na

H2O

H
R

NaOH
H2O

O
C6H5SNHR
O

N,N- .
, .. .

- N,N- .
C6H5SO2Cl + R2NH

NaOH
H2O

C6H5SO2-NR2

,
N--N,N-
- :
C6H5SO2Cl + R3N

[C6H5SO2-NR3] Cl

NaOH
H2O

C6H5SO2-ONa + NR3

1632

1633

R3N + HCl

R3NH Cl

, 1935
, -N264S2N2
.

. .
, ,
. ,
- ,
. ,
.
, .
.
, ,
, -,
,
.
.
NH2
H2N

N N

SO2NH2

( )

H2N

SO2NH2 + H2N

NH2
NH2

( )

-,
-N264S2N.
, ,
.
, , ,

1633

1634

, , .
,
,
.
.
N
n-NH2C6H4SO2NH

OCH3

n-NH2C6H4SO2NH

OCH3

CH3
N

n-NH2C6H4SO2NH

N
S

n-NH2C6H4SO2NH

C2H5

CH3

:
C6H5NH2

(CH3CO)2O

CH3CONH
HCl; t o
H2O

NH2

C6H5NHCOCH3
SO2Cl

ClSO3H; t o

NH2X

CH3CONH

SO2NHX

SO2NHX

" " (
.)
.

, .
, .
.
,
"".
, .

1634

1635

OH
N

N
H2N

O
C NH CH COOH
CH2 CH2 COOH

CH2 NH

N
-

).

, .
-
(.21.1), "
" ,
. , "" ,

. -
.
H

6,9 A

6,7 A

C
H O

S O
NH2

2,3 A

2,4 A

. 21.1. -

. ,

1635

1636

.
.
NH2
N

N
H2N

O
C NH CH COOH
CH2 CH2 COOH

CH2 N
CH3

21.6.5.

, .
.

N- .
0-5 oC

2R3N + 2HCl + NaNO2

R3NH Cl + R3N-N=O
Cl

N- 0 ,
N

, .

N-
R2NH + HCl + NaNO 2

0-5 oC
H2O

N-
0-5 oC

(CH3)2NH + HCl + NaNO2

R2N-N=O + NaCl + H2O

H2O

(CH3)2N-N=O (88%)

:
6H5NHCH3 + HCl + NaNO2

0-5 oC
H2O

C6H5N-N=O
CH3 (90%)

N- ,
,

1636

1637

, ,
, .
N-,
, .


, -100

("")

,
""

-.
, ,
, -.
CH3(CH2)3NH2 + NaNO2 + HCl

0oC

CH2=CHCH2CH3 +

H2O

(26%)

+ CH3-CH=CH2-CH3 +
(10%)

+ CH3(CH2)3OH + CH3CHCH2CH3 +
(25%)

OH (13%)

+ CH3(CH2)3Cl + CH3CHCH2CH3
(5%)

Cl

(3%)

,
""
.
,

,
.
ArNH2 + 2NaNO2 + 2HX

0-5 oC
H2O

Ar-N=N X + 2NaX + 2H2O

22.

1637

1638

,
,
, ,
, , ,
,
.

21.6.6.

.
0-5 oC

RNH2 + 2NaOCl

H2O
0-5 oC

R2NH + NaOCl

H2O

RNCl2
R2NCl

-.
R2NH + (CH3)3COCl

0 oC

R2NCl + (CH3)3COH

21.6.7.

-
. .
R3N + H2O2

R3N

O + H2O

30%-

.
(C2H5)3N + H2O2

30% H2O2
0-20 oC

(C2H5)2NCH2CH2N(C2H5)2 + H2O2

(C2H5)3N

0-20 oC

O (95%)

(C2H5)2NCH2CH2N(C2H5)2
O (92%) O

1638

1639

N(CH3)2 +

CO3H

CH2Cl2
0 oC

N(CH3)2 +
O

Cl
CH-N(CH3)2
CH3

30% H2O2
H2O

(90%)

CO2H

Cl

CH-N(CH3)2
CH3

(98%)

N- ,
.
. N-
.
. 1906

O
C6H5 N
CH3CH2 CH3
N-
.
N-
N,N-
40 80%:
NH + H2O2

HCOOCH3

N OH (78%)

,


:
RNH2

RNH-OH

CH3

NH2

NH2

RN

CH3CO3H
H2O

CH3

CH3CO3H
CH2Cl2

1639

OH

R-N=O

OH

N=O (73%)

N=O (62%)

1640

-

H3SO5

C6H5CH-NH2

C6H5CHNO

CH3

C6H5C=NOH

CH3

CH3

-
.

.
, - - (. 22).
O2N

NH2

CF3CO3H
CH2Cl2
50 oC

NO2
O 2N

NH2

CF3CO3H
CH2Cl2
50 oC

O2N

NO2 (88%)
NO2

O 2N

NO2 (86%)

Cl

Cl
Cl

NH2
Cl

CH3

CH3

CH3

C CH2

CH3

NH2

CF3CO3H
CH2Cl2
50 oC

CH3

NO2 (92%)

Cl
Cl

KMnO4
-
50 oC

CH3

CH3

CH3

C CH2

CH3

NO2

CH3

(69-82%)

21.6.8.

1640

1641

NR4 Hal + AgOH

H2O

NR4 OH + AgHal

.
2- . 1851

100-150
.
( 10),

.
N(CH3)3 OH
CH3

100-120 oC
H2O

CH2 +

CH3 +
1%

99%

+ N(CH3)3 + H2O
120 oC

CH3(CH2)3CHCH3
N(CH3)3 OH

H2O

CH3(CH2)3CH=CH2 +
98%

+ CH3CH2CH2CH=CHCH3 + N(CH3)3 + H2O

2%

,
,

- -,
,
, 4:1.
-,
( 24).
, ,

, ..
, :

1641

1642
120-140 oC
H2O

(CH3CH2CH3)2N(CH2CH2CH2CH3)2OH

CH3CH=CH2 + CH3CH2CH=CH2 + H2O + C3H7N(C4H9)2 + (C3H7)2NC4H9

63%

37%

,

150 oC

1) CH3I
2) AgOH

H2O

N (CH3)2 OH

N H

1) CH3I
2) AgOH, H2O, 120 oC

N(CH3)2

+ N(CH3)3 + H2O
1,6-

, .
1911 . .
O
CH3N

OH

Na
CH3CH2OH

CH3N

H2SO4; CH3COOH; t o
-H2O

(84%)

(CH3)3N

(CH3)2N
CH3I

(CH3)2N

AgOH; H2O; t o

Br2
CHCl3
1,6-

I
AgOH; H2O; t o

CH3I

(95%)

(90%)

(96%)

(CH3)2N

Br

CH3I

(CH3)2NH
-2HBr

Br

N(CH3)2
(68%)

(72%)

(CH3)3N

CH3N

I
AgOH; H2O; t o

(97%)

N(CH3)3 I

+ 2N(CH3)3 + 2H2O
(10-20%)

(N), .

1642

1643

1,3,5,7. ,
90%, ,
, 3%.

N,N- N- . (., 1949
.).
R1
R2

R3
R4

N(CH3)2

R2NOH

R1

100-150 oC

R2

R3 + (CH3)2NOH

R4

R2N+-O-
. N-

-.

2~ - .

N- , , ,

.
CH3

CH3
O

120-150 oC

CH3
+

+ (CH3)3NOH

N(CH3)2
CH(CH3)2

CH(CH3)2
C6H5 O N(CH3)2
CH CHCH3
CH3

64%

120 oC

C6H5
CH3

CH(CH3)2

C CHCH3

+ (CH3)3NOH

1643

36%

C6H5
CH3

CH CH CH2

1644

, .

21.7.

(.
.13).
.

21.7.1.

, ,
.
,
2,4,6-.
- -

- - , :
Br

NH2
H2O

Br2 +

Br

40 oC

Br

COOH

75%

COOH

COOH

COOH
NH2 + Cl2

NH2

H2O
40 oC

NH2 69-78%

Cl
Cl

.
.

1644

1645

NH2

(CH3CO)2O

NHCOCH3

Br2
CH3COOH
50 oC

Br

NHCOCH3

H3O

Br

NH2

pa-
.

21.7.2 .

,
.
.
.
NHCOCH3

HNO3
H2SO4

NHCOCH3 +

O2N
90%

NHCOCH3

90%-
. HNO3O 2N

NHCOCH3 +
77%

HNO

3
O2N
NHCOCH3 (CH CO)
3
2O

20 oC

NHCOCH3

NHCOCH3
23%

NHCOCH3 +
30%

NO2

NO2
NHCOCH3

70%

NO2

-
- . , ,
. -
-
-. 2--4-
60%- -.

1645

1646

HO3S
NHCOCH3

H2SO4

HNO3
H2SO4

NHCOCH3
HO3S

NHCOCH3

H2O
+
H

NH2
56%

NO2

NO2

, ,
.
N(CH3)2

HNO3

N(CH3)2 + O2N

CH3COOH

NO2

N(CH3)2
2

21.7.3.

" ".
,
180-200.
, .
NH3 HSO4

NH3
180 oC

SO3
- , , ,

.
.
.

1646

1647

-,
,
.

21.7.4.

-
. , 1927 ,
.
(CH3)2N

+ HCN(CH3)2
O

1) POCl3
2) H2O

CHO

(CH3)2N
80-85%

-,
.
SOCl2.

.
,

.
O
O
H C

O
+

N(CH3)2

P Cl
Cl
Cl
O

H C

Cl
Cl

Cl

N(CH3)2

Cl
H C N(CH3)2

Cl
H C
Cl N(CH3)2

Cl

Cl2PO2

,
NR2, NHR, OR, .

1647

1648

-
.
NR2

NR2
- H+

+ ClCH=N(CH3)2
H

CH-N(CH3)2
Cl

NR2

NR2

H2O; CH3COONa
H2O; 60 oC

CH

Cl

CHO

N(CH3)2
, .

.

, .

21.7.5.

()
-
-.
NR2

NaNO2 + HCl
0-5 oC H2O

O=N

NR2 (80-90%)

,
, -

,
N,N----.

1648

1649

N-,
.

NHR

NaNO2 + HCl
0-5 oC

N
R

O
(87-93%)

N- HCl
-:

O=N

C2H5OH

HCl

NHR

- -
, .

22.

21.8.
,

.
1. .
2.

.
3. ,
.
- CH3CO;
HCO; 65; ..
(
, bz) -

1649

1650

().

0-10 .
-
0-10 oC; NR3

RNH2 + Cl-C-OCH2C6H5
O

RNH-C-OCH2C6H5 + HN(C2H5)3Cl
O

d/ ,
r .
Pd/C
20 oC

RNH-C-OCH2C6H5 + H2

RNH2 + CO2 + C6H5CH3

C6H5CH2OH + COCl2

0 oC

O
C6H5CH2O-C-Cl + HCl
(95%)

- () - ---:
O

RNH2 + (CH3)3C-O-C-O-C-OC(CH3)3

N(C2H5)3

O
(CH3)3C-O-C-NHR

-
HCl r 0-20,
.
,
.
O
C
O + RNH2
C

N(C2H5)3

C
NR
C
O

1650

1651

O
C

20 oC

NR + NH2-NH2

C2H5OH

C
RNH2 +
C

NH
NH
O

, .
.
O

RNH2 + CF3C-SC2H5

0 oC

O
RNH-C-CF3 + CH3CH2SH

.,

. .,

/.

-6.5

0,769

3NH2

-93

-70 oC

C2H5NH2

-81

16,5

0,706 o

C3H7NH2

-83

49

0,72

(3)2N2

-101

34

0,694

3(2)3NH2

-50

77

0,74

H3C-CH(NH2)-CH2CH3

-104

63

0,724

(CH3)3CNH2

-68

45

0,696

(3)22NH2

-85

68

0,736

1-

CH3(CH2)4NH2

-55

104

0,761

1-

CH3(CH2)5NH2

-19

133

0,763

1-

CH3(CH2)6NH2

-23

158

0,777

1-

CH3(CH2)7NH2

179

0,77

-611NH2

134

3(2)15NH2

322

C6H5CH2NH2

185

(1-)
2-
(-)
-

(1--2-)

1651

1652

-96

7.5

0,680

-50

55,5

0,710

-40

111

0,738

-61

84

0,722

-70

140

0,745

-59

159

0,767

254-256

-124

3,5

0,662 -5 oC

-115

89,5

0,723

-93

156

0,757

214

0,778

1652

1653

22
,

22.1. ..................... 1653
22.1.1. .............................................................................. 1654
22.1.1.. .......................................................... 1655
22.1.1.. ................................................................................ 1660
22.1.2. ................................................................................................................... 1661
22.1.2.a. .......................................................................................... 1661
22.1.2.. .............................................................................................. 1664

22.2. ........................................................................................................ 1671

22.2.1. .............................................................................. 1671
22.2.1.. ................................................................................. 1672
22.2.1. .
........................................................................................................................... 1673
22.2.3. .......................................................................................... 1673
22.2.4. ............................................................... 1678
22.2.4.. ..................................................................... 1680
22.2.4.. ............................................................................ 1681
22.2.4.. ........................................................ 1683
22.2.4.. -, -, -, - (
)............................................................................................................................... 1684
22.2.4.. - .......................................... 1685
22.2.4.e. . ................................... 1686
22.2.5. ...................................................... 1692
22.2.5.. -
........................................................................................................................................ 1692
22.2.5.. ( -).............. 1695
22.2.5.. ................................................................. 1701
22.2.5.. ..................................................................... 1701
22.2.3. ....................................................... 1701
22.2.4. ............................................................................................... 1704
22.2.5. ........................................ 1707
22.2.6. ,
.............................................................................................................................. 1707
22.2.7. () .................................................. 1708
22.2.7.. ........................................................................................... 1709
22.2.7.. ............................................................................................ 1711

22.3. - ............................................... 1713

22.4. .................................................................................................................................... 1714
22.4.1. .......................................................................................................... 1715
22.4.2. ............................................................................................................. 1716
22.4.2.. .......................................................................... 1716
22.4.2.. 1,3- ....................... 1717

22.1.
N

O
O .

1653

1654
. 10,2, ..
- .
:
8,5; 2- 7,7, .. 2-

-,

, -,

RCH N
:

O
O

( 13
15).

22.1.1.

13.

.
90%-
. ,
.

, - -
: - , - -,
1,2,4-, 2,6- .

O2N

NH2

(CF3CO)2O; H2O2
CH2Cl2; 40 oC

O2N

NH2

(CF3CO)2O; H2O2
CH2Cl2; 40 o C

O2N
O2N

86%

NO2 88%
NO2

NO2

Br

Br
Br

NO2

NH2

(CF3CO)2O; H2O2
CH2Cl2; 40 oC

Br

NO2 100%
Br

Br

1654

1655

22.1.1..

- ,
.
(SNAr). ,
, 1,2,4- -,
- :

NO2

NO2
O 2N

NO2 + C6H5NH2

NR3

O 2N

NHC6H5

87%

. .
.

.
98%.

C6H5NO2 + 3H3

Cu/SiO2
350-370 oC

C6H5NH2 + 2H2O
98%

.
250-300 .
97-98%.
.
,
.

. 1842
..,
.
,
.
,
.
(, ) .
(II) . ,
C; R; R .,
.

1655

1656

.

NO2

NHOH

N=O
+2e; +2H+;
-H2O

NH2

+2e; +2H+

+2e; +2H+

+ H2O

-

.
.
-
.

ArNO2 + K

ArN

-.

O- K

+ K

ArN

ArN

O K

O K

O
OH

- H2O

ArN

+ 2H+
H2 O

Ar-N=O

OH
, ,
N-.
,
.

N-

N-

Ar-N=O

+e

Ar-N-O

+e

Ar-N-O

+ 2H+

Ar-NH-OH

1656

1657
-
:

Ar

_
N OH + 2e + 2H

ArNH2 + H2O

.

.
:

C6H5NO2 + Zn + H2O

NH4Cl
H2O; 65 oC
pH = 7,5-8,5

C6H5-NH-OH + Zn(OH)2
62-68%

C6H5NH2.HCl + ZnCl2 + H2O

C6H5-NH-OH + Zn + HCl

90%

,
, :

C6H5-NH-OH

K2Cr2O7; H2SO4
H2O; 5 oC

C6H5N=O
70%

, , ,

, .
.

O
ArN=O

Ar-N-N-Ar

.

.
:

C6H5N-OH
H

OH

1657

C6H5N-OH

1658

C6H5N-OH + C6H5N=O

OH O

C6H5-N N-C6H5

O
C6H5-N N-C6H5 + OH

s2O3 :

O
C6H5NO2 + As2O3

NaOH
H2O; 80 oC

C6H5-N=N-C6H5 85%

, .

O
C6H5N=N

C6H5

Zn; NaOH
CH3OH; 70 oC

C6H5N=NC6H5

84-86%

C6H5N=NC6H5 + Zn + NaOH CH OH; 70 oC

3

C6H5-NH-NH-C6H5 88%

. ,

-.

,
:

O
C6H5N=N

C6H5

P(OR)3
H2O2; CH3COOH; 60 oC

Pd/C, NH2-NH2
O2 NaOCl

C6H5N=NC6H5

C6H5NH-NHC6H5

- -.
-, -
-.

C6H5

C6H5

t oC

N
C6H5

N
C6H5

- 25
.

1658

1659

.
1

Ar N=O + Ar NH2

Ar N=NAr + H2O

, .
LiAlH4

ArNO2

ArN=NAr

.
, ,
. - . , ,

(II) :

C6H5-N=N-C6H5 + 2Na2S2O4 + 4H2O

2C6H5NH2 + 4NaHSO3


:
:

ArNO2

ArNO

ArNH-OH

ArNH2

ArNO2

ArNO

O
ArN=N-Ar

ArNH-OH

ArN=NAr

ArNH-NHAr

,

.

4C6H5NO2 + 9Fe + 4H2O

4C6H5CH2 + 3Fe3O4

, , - 2,4-.

NO2
O2N

+ NaHS

NH2
CH3OH

1659

O2N

80-85%

1660

NO2
O2N

NH2
H2S NH3
C2H5OH

NH2

O2N

NH2
52-58%

ArNO2 + 4Na2S + 4H2O

ArNH2 + Na2S4 + 6NaOH

- -
. ,
, .

4ArNO2 + 6NaSH + H2O

4ArNH2 + 3Na2S2O3

22.1.1..
4,4-, ,
1845 ...
.
,

, 70%
30% 2,4- ().

H2N
H2SO4
.

NH NH

H2N

NH2 + H2N
70%

30%

2,2

(-).

- ,
( ).

NH NH

HCl
CH3OH

NH2

NH

X = Cl; Br; RO; R

12

, .

, .

1660

1661
.
, .
,
.
:

H2N
+ 2H+

NH NH

H2N

NH2

H2N

NH2
- 2H+

NH2

H2N

NH2

, ,

0,15
- .
-
.

[5,5]- (. 25 26).
.
.
.

22.1.2.

.
.

22.1.2.a.
50%-70%-
500-700 300-500
,
(. 4)
.
.

1661

1662

-, . 1872 .
.
, 0-20,
.

RBr + AgNO2
-

0-10 o C

RNO2 + RONO + AgBr

( ),
. -
-
, .
N- O- (/)

. 75%-85%,
15%-18% 5% . ,
,
. , ,
, -
.

RCH2Br + AgNO2
ArCH2Br + AgNO2

0-20 o C

RCH2NO2 + RCH2ONO + AgBr

0-10 o C

ArCH2NO2 + ArCH2ONO + AgBr

RCHCOOC2H5 + AgNO2
I

75-80%

40-84%

20 oC

20-25%

60-16%

RCHCOOC2H5 + AgI
NO2 75-85%

,
,
. , ,.
. (1955 )
, ,-
.
.
,
,
.
60%, .. , (75%-80%).
:

1662

1663

CH3CH(CH2)nCH3 + NaNO2
25 oC

Br

CH3CH(CH2)nCH3 + CH3CH(CH2)nCH3 + NaBr

55-60%

NO2

ONO 25-30%

. - -
60%-80%
.

:
(CF3CO)2O; H2O2
CH3CN

NOH

NO2

60%

- ,
.
- :
CH3CO3H
CH2Cl2

NH2

NO2

70%

.
80-85:

ClCH2COONa + NaNO2

85 oC
H2O

[O2NCH2COO Na ]

85 oC
H2O

CH3NO2 + CO2 + NaHCO3

35-38%

. -
.
.
.

RCH2COOH

2LiH(C3H7-i)2

RCHCOOLi
Li

R-CH-COOH

1) C3H7ONO
2) H3O+

RCH2NO2 + CO2
45-65%

NO2

,. -
.
,-.

1663

1664

O
N O
1) 2KNH2; . NH3
2) 2RONO2

H3O

O2N(CH2)5NO2
90%

N O
O

- :

ArCH2COOC2H5
+

H3O

1) C2H5OK
2) RONO2

ArCH=NO2K + (C2H5O)2CO

ArCH2NO2 80%

22.1.2..
1.
-
, :

O
RCH2N

RCH=N

OH

.
20 1.10-7 ,
2- 3.10-3. -
. - -
. -
.
. 1896
.
. 0

, - -.

(III)
. - .
, , ,
. , ,
, 2- -
, 15-30 0 -
- .

, -
-. a

1664

1665

CH2=N O
OH ~ ,2. 2-
~10,2, -
, a (CH3)2CHNO2 7,68, (CH3)2C=NOOH a 5,11.
a (. 3),
- O- , - -.
, -
, -
-. , .
2).
-, - ,
,
.

O
RCH2N

B
BH

RCH

+ BH
BH
OH

RCH=N

OH

. ,
-.

, - ,
-.
,
, .

, .
NaOH
RCH2NO2 1)
2) Cl2; H2O; 0 o C

RCHNO2
Cl

RCH2NO2

NaNO2; H2SO4
H2O; 0 o C

RCHNO2
N=O

RCHNO2

N-OH
:

1665

H3O ; H2O

1666

NaNO2; H2SO4
H2O; 0 o C

R2CHNO2

N=O
R2C

NO2

+ H2O

, .
.
. 0
.
,
,
-,
. 20
- .

O
RCH2Br + (CH3)2C
t oC

2H5OH

O
(CH3)2C N

O CH R

(CH3)2C=N-OH + RCHO

,
.
,
.

2-

O
(CH3)2C

+
O Na

t oC

(CH3)2C N

CH2Z

O CH

O
(CH3)2C=N-OH +
X

C
H

, .

1666

1667

O
(CH3)2C

+ RCH=CH-CH2X

(CH3)2C N

O Na
t oC

O CH CH=CHR

O
(CH3)2C=N-OH + RCH=CH-C H

, -
--.

. -

0-(-20).

R
R

1
2

O
C

+ R3O BF4

CH2Cl2;
0-(-20) oC

1
2

O
C N
80-95%

OR

+ R2O

- - .
. -

-
- .
SRN1 ,
( 15).

(CH3)2C=NO2 + n-NO2C6H4CH2Cl

(CH3)2C=NO2 + n-NO2C6H4CH2Cl

n-NO2C6H4CH2Cl

n-NO2C6H4CH2 + Cl

n-NO2C6H4CH2 + (CH3)2C=NO2

n-NO2C6H4CH2-C(CH3)3NO2

n-NO2C6H4CH2C(CH3)2NO2 + n-NO2C6H4CH2Cl
n-NO2C6H4CH2C(CH3)2NO2 + n-NO2C6H4CH2Cl ..
- -
. 1970-1975

, , ,-

- , - .

NO2
(CH3)2C-COOC2H5 + (CH3)2C=NO2
NO2

(CH3)2C-C(CH3)2 95%
COOC2H5

1667

1668

CN

CN

C(CH3)2 84%
NO2

NO2 + (CH3)2C=NO2
NO2

NO2

NO2 + (CH3)2C=NO2

C(CH3)2 91%
NO2

,
.

Br

NO2
NO2

NO2 +

89%

NO2
-
.
- -100.

RCH2NO2

2 -C4H9Li
; -100 o C

RCH=N

1) R Br

2) H3O+

CH-NO2

-
.

RCH=N

O
O

1) R COX; ; - 78 o C
2) H3O+; -78 o C

O
1

R C-CH-NO2
R

- -
,

-.
-,
.
O

RCH2NO2

1) CH3O-Mg-O-C-OCH3
2) H3O+

RCHCOOH
NO2

3. ( )

- , .

1668

1669
KOH
C2H5OH; 0 oC

CH3(CH2)7CHO + CH3NO2

C6H5CHO + CH3NO2

CH3(CH2)7CH-CH2NO2
OH

NaOH KOH
C2H5OH-H2O; 25 oC

80%

C6H5CH=CH-NO2
75%

. 1895
- .
, ,
(a ~ 10) (a
~ 20). ,
.
, .
,
.
.
4.
.
, , ,
-.

O
R2C

+ CH2=CH-X

R2C-CH2CH2X
NO2

O
X = C ; COOR; CN
R

2=.
. -

.
.

R
RC=CH2 + RCH2NO2
NO2

C2H5O Na
C2H5OH

1669

RCHCH2-C-NO2
NO2

1670


.

OH
CH3COCH3 + CH3NO2
(CH3)2C=CHNO2

(CH3)2C CH NO
2
2
CH3NO2

- H2O

(CH3)2C(CH2NO2)2

.
1

R2NH + HCHO + R2CHNO2

R2CCH2NR2 + H2O
NO2

.
5.
-
.
, .

O
2 RCH

+ 2H+

O
O
2 R2C

+ 2H+

H2O
0-5 o C

H2O
0-5 o C

2RCHO + N2O + H2O

70-80%

2RCOR + N2O + H2O

80-85%

. 1894 .
, .

HOCH2(CHOH)4CH2NO2

2H3O+
H2O; 0 o C

NaOH
NO2 1) H
+
2) 3O ; H2O; 0 oC

C6H5

HOCH2(CHOH)4CHO
70%

81%

C6H5

. ,
- .

1670

1671

OH
R1 C R2
O

R1 C R2

OH

OH

-H2O

R1 C R2
N

HO

H2O

R1 C R2

-H

OH

HO

OH

O
2
R C R + N2O + H2O
1

R C R
N

,
2. 30 . .
, 85%-90%-
.
.
H2SO4; t oC
H2O

RCH2NO2

RC

O
NHOH

H2O
H3O+

RCOOH + NH2OH

RCH2NO2
+

H+

RC=N-O
H OH
O

RC
NHOH

RCH=NOOH
H

RCH=N

RC N-OH

H
H+
H2O

H+

OH
OH

H2O

RCOOH + NH2OH

22.2.
,
.
.

22.2.1.
,
-N=N- , .
C6H5N=N-NHC6H5,
C6H5N=N-OC6H5. ,
, , n-NH2-C6H4N=N-C6H5 - .
Ar-N

N X . , - - Cl-,

1671

1672
Br-, HSO4- : BF4-, SnCl62-, PF6-, SbF6-, HgCl3- ..
,
-.
,
.

22.2.1..


.
- Ar-N

N X .

0,32 ,
, , . ,
.
:
(+ 0,270), (+0,5842) -
.

N N .

--

+0,89 +1,56. , -
- .
- n-X-C6H4N2+
X, +-. , ,
262

C6H5-N N 314

n-CH3O-C6H5-N N . -

ArN2+
AlkN2+,
Alk+.

. BF4-, SbF6-, HgCl3- .

20 . , ,
,
. - - -
,
.

1672

1673

22.2.1. .


. 1858 .
.

.
.

ArNH2 + NaNO2 + 2HCl

ArN NCl + NaCl + 2H2O

. ,
,
0,5-1,5. ,

, , .

ArN N + H2N-Ar
ArN N +

ArN=N-NH-Ar

Ar-N=N

NH2

NH2

. -
, ,
. , , ,
0-5. .

. - 2,4-, 4--2,6, .
- 20.
.

2 H2SO4 + NaNO2

ONOSO3H + NaHSO4 + H2O

22.2.3.
,
.

1673

1674
. . .
(), . () ..- ().

.
-:

HNO2 + H3O

H2O + H-O-N=O
H

- . ,
,
, .

H2NO2 + NO2

O=N-O-N=O + H2O

H2NO2 + Cl

O=N-Cl + H2O

H2NO2

O=N-Br + H2O

+ Br

: ,
.
, . , , ,
+N=O ,
N2O3.
, ,
.
.
.

NaNO2 + 2H2SO4

0-20 oC

O=N-OSO3H + NaHSO4 + H2O

NO+ >> H2NO2+ >

NOBr > NOCl > N2O3 >> HNO2.
.
, ,
.
- , .
,
.
,
.

ArNH2 + H3O

ArNH3 + H2O
1674

1675
.
N-,
. 1900 .

(1) ArNH2 + O=N-X

X = Cl; Br; ONO

Ar-N-N=O + X
H H

, ,
.

(2) ArNH2-NO + H2O

ArNH-N=O + H3O

(3) ArNH-N=O + H3O

H
(4) ArN N=OH + H2O

ArNH-N=OH + H2O
ArN=N-OH + H3O

(5) ArN=N-OH + H3O

H
(6) Ar-N=N-O

H
Ar-N=N-O

+ H2O

ArN N + H2O

(4) ,
.
- ,
- .
IV.
.
,
- (103-105),
OH-, OR- . .

ArN2 + X

ArN=N-X

( ).

ArN2

+ OH

k1

ArN=N-OH

, , ,
, -
-:

Ar-N=N-OH + OH

k2

1675

ArN=N-O

+ H2O

1676
:

ArN2 + 2H2O

k1

ArN=N-OH + H3O
k2

Ar-N=N-OH + H2O

ArN=N-O

+ H3O

, k2
> k1. .
,
k2 k1 .
11-13, 9-10.
, 12, C6H5N2+ C6H5-N=N-O-
, =7 .
, ,
, , -, .
- - -,
-(-) -(-).
- ,
-.

O
N
N

N
N
+ 2OH

H2O

H2O; H+

c-

- -
.

2,4-
-. -.
- -
140.
-
- . - N, .. -- :

Ar

N N

+ H3O

ArNH N O + H2O

N- ,
(2)-(6) . -

1676

1677
.
:

N N

Ar

H3O+

O
Ar

+ H3O
N N

H
O H

N N

Ar
Ar

OH + H2O

N N

+ H2O

- - - , -
-
. - N.
, , - .
-.

(..-, .):

Ar

N N

Ar

N N

OH
H

OH

t oC

N N

Ar

Ar N N OH

OH

Ar NH N OH

N-

OH

OH

Ar NH N OH
,
. 1894 .
.
-
, .
- ^-,
:

O Na
N N

+ RI

Ar

20 oC
CH3OH

O Na
N N
Ar

+ (C2H5)3OBF4

Ar

N N O + NaI
R 70-80%

-20 o C
CH2Cl2

N N
Ar

OC2H5

60-70%

,
:

1677

1678

OAg
+ RI

N N

OR

N N

-10 o C

Ar

Ar

-
-.

N N
Ar

O K

-20 oC

+ (C2H5)3OBF4

N N

CH2Cl2

C2H5

Ar

N-

O
Ar N N O Na

0 oC

+ RCOCl

C R
Ar N N OC2H5
20-80%

N- O--

N O
Ar N
C

t C

Ar

N
O

Ar

N
N

O
C
O

, ,
.
(PF6-, SbF6-, BF4-)
: .
. ArN

NX ;

X- = PF6-, SnCl62-, BF4-, ZnCl42- . - -

ArN=N-SO3- Na+ ArN=NCN. -,
.

22.2.4.
.
,
:
ArOH, ArSH, ArI, ArBr, ArCl, ArF, ArCN, ArNO2, ArH,
Ar-Ar, Ar1-Ar2, ArN3, ArNH-NH2, Ar1N=NAr2 .

1678

1679
,
-:

1679

1680

X + N2

(1)

+ N2 + X.

(2)

N2 + X
Y

N=N-X

(3)

N2 + Y

(4)

X
(I) (4) .
,
. , ,
Y - - Y .
(1) .
(2). r

.
.
.
1. ,
.
, ,
15. -
. -N : , -
.
- ,
, (I-, SCN-, SH- .).
,
. .

,
.

22.2.4..

ArN2 X + H2O

t oC
H2O

1680

ArOH + N2 + HX

1681
40%-50%- .
, ,
40%-50%- .
, SN1
15, :

CH3

H2O

N N

100 o C

H2SO4

CH3

Br

92%
H2O

N N

Br
OH

100 o C

H2SO4

O2N

O2N

81-85%
H2O

NaNO ; 5 oC

OH H SO 2; H O;
2
4
2

N N H SO 100 oC
2
4
CHO

(CH3O)2CH

(CH3O)2CH

OH

OH
78%

,
-
- . SN1- ,
, , , .

ArN2

Ar +

2H2O
ArOH

N2
Cl
ArCl

+ H3O

-,
- . r+ SO4 rOSO3H
.

22.2.4..

:

ArN BF4

t oC

ArF + BF3 + N2

, . 1927 , -,
.
.

1681

1682

NH2

HNO2
HBF4

CH3

N2 BF4

200 oC

CH3
BF4 N2

CH3
N2 BF4

180 oC

F + N2 + BF3
69%

F
82%

. ,
,
.
:

1682

1683
H2O

ArN2 Cl + HPF6

ArN2 PF6

+ HCl

, , . , ,
-
61%,
9%.

NH2

NaNO2
HCl

N2 Cl HPF6

N2 PF6

COOH

COOH

170 oC

F
61%

COOH

COOH

- 40% ,
15%.
180 oC

N2 SbF6

F
40%

NO2

NO2
N2 BF4

180-200 oC

F
NO2

NO2

10-15%

--:

NH2

NaNO2
HCl

N2 Cl HPF6
Br

Br

N 2 PF6
94-97%

165-170 oC

Br

F
78%

Br

22.2.4..

- ,
.
, - ,
15.
.

C6H5N2 Cl

O2N

KI
H2O; 25 o C

NaNO2

NH2 H SO ; H O O2N
2
4
2

C6H5I + N2 + KCl
74-76%

N2 Cl

5 oC

1683

KI
O2N
H2O;
30-40

I
81%

1684

KSCN
H2O; 25 oC

C6H5N2 Cl

C6H5-C-C N
54%

22.2.4.. -, -, -, -
( )
,
-, - -
20%. . (1884 .),
, -, - -
(I).
, Cu2Cl2,

u2Br2. l u2Br2 r Cu2Cl2
.
Cu 2Br2
HBr; 60 o C

NaNO2
HBr; 0-5 oC

Cl

NH2

Cl

N2

NaNO2
HCl; 0-5 oC

CH3

NH2

CH3

+ N2
Cl

Br
80-95%

Cu 2Cl2
HCl; 70 o C

N2

+ N2
CH3

Cl
74-79%

1) NaNO ; HCl; H O

NH2 2) Cu Cl 2; 80 oC 2
2 2

Cl
Cl

NH2

70%

.
, (I)

.
- r , e ArN=N ,
:

ArN2 X + CuIX

[Ar . CuIIX2] + N2

ArX + CuIX

,
X- .
SRN1 -
( 15) , (I).
, -
(I) .

1684

1685
, .

Cu(I) + ArN2 + 3X

Cu

2-

N=N-Ar

ArX + N2 + Cu(I) + 2X

-
(I) -.
Cu(CN)2-, :

CH3

CH3
NH2

NaNO2
H2SO4; H2O; 5 o C

N2 HSO4

64-70%

NO2

NO2
NH2

CH3
K[Cu(CN)2]
H2O; 5 oC

NaNO2
HCl; H2O; 0-5 o C

N2 Cl

CN
NO2

K[Cu(CN)2]
H2O; 90-100 oC

CN

65%

. (1890 ), -
.

CH3

CH3
NH2

NaNO2
HBr; H2O; 0-5 oC

N2 Br

CH3
Cu
H2O; 50 o C
43-47%

Br

-:

O2N

N2 BF4

NaNO2; Cu
H2O

O2N

NO2
67-82%

47

,
.
-
(. 21). -
- , - -

22.2.4.. -
N3 SH-
-

1685

1686
,
.

Ar

Ar

N N + NaN3
Cl

t oC

N + NaCl
N N

Ar-N=N=N

+ N2

NH2

N3

N2 Cl
NaN3

NaNO2;
HCl; H2O

88%

,
. SH-
. , z
, ,
:

CH3

CH3

CH3

NH2

KS

NaNO2;
HCl; 0-5 o C

S
C OC2H5

H2O 40 oC

N2 Cl

CH3

S
C OC2H5

CH3
HCl

KOH;
H2O; 80 o C

63-75%

SK

SH

22.2.4.e. .

, , , , :
HCl
H2O

ArN2 Cl + HgCl2

ArN2 HgCl3

ArN2 Cl + SbCl3

HCl
H2O

(ArN2 )2 SbCl52-

ArN2 Cl + BiCl3

HCl
H2O

(ArN2 )2 BiCl52-

.. (1929 .),

: , , , ,
, .
"" ...

1686

1687

n-IC6H5N2 HgCl3

-10 oC

+ 2Cu

n-IC6H4HgCl + N2 + Cu2Cl2
45%

2-(n-C2H5OOC-C4H6N2) HgCl3 + 6Cu + 6NH3

0 oC

(n-C2H5OOC-C4H6)2Hg + 3Cu2Cl2 + 2N2 + Hg

88%

(C6H5N2 )2SbCl52- + 2Zn

CH3COOC2H5
77 o C

20 o C

3C6H5N2Cl.BiCl3 + 2Bi

46%

(C6H5)3Bi + 3N2 + 4BiCl3

50%

5-15 oC

4C6H5N2 BF4 + 3Pb

(C6H5)2SbCl + N 2 + 2ZnCl2

(C6H5)4Pb + 2Pb(BF4)2 + 4N2

15%

, , ,
,

.
CF3COOH

Ar Cl + Ar N2 PF6

5-15%

CF3COOH

Ar Cl Ar PF6 + N2

Ar Br + Ar N2 PF6

Ar Br Ar PF6 + N2
6-12%

,
15-20%.

-:

ArH + BrF3

CH2Cl2
-70 oC

(C2H5)2O.BF3
CH2Cl2; -70 oC

[ArBrF2]

ArH
CH2Cl2; -70 oC

Ar2BrF

Ar2Br BF4 + (C2H5)2O

15-50%

CH Cl ; -70 oC

2ArHg + BrF3 (C 2H )2 O.BF

2 5 2
3

Ar2Br BF4 + (C2H5)2O + 2ArHgF

60-99%

, .

() . 1886
.

C6H5I + Cl2

CHCl3
0 oC

C6H5ICl2

87-94%

().

1687

1688

C6H5ICl2 + 2NaOH

H2O
20 o C

C6H5I=O + 2NaCl + 2H2O

54%

100
().

2C6H5I=O

100 o C
H2O

O
C6H5I + C6H5I

92-95%

,
(()).

C6H5I + CH3CO3H + CH3COOH

30 oC

C6H5I(O-C
98%

)2

CH3
O

C6H5I + CF3CO3H + CF3COOH

C6H5I(O-C

)2

CF3

(III) - -,
,
- (III)
().

C6H5I(OCOCH3)2 + 2NaOH

C6H5I(OCOCH3)2 + CH3

H2O
20 oC

C6H5I=O + CH3COONa + 2H2O

85-90%

Cl(CH2)2Cl

SO3H

C6H5I
88%

OH
OTs

+ 2CH3COOH

,
-
.

+ 2C6H5I

OH

OTs

CH2Cl2

+ 2C6H5I + H2O

OTs

OTs

ArNH2 + 2C6H5I(OCOCH3)2

ArN=NAr + 2CH3COOH + 2C6H5I

55-90%

1688

1689

,
:

OSi(CH3)3

O
1) LiN(-C3H7)2
2) (CH3)3SiCl;

OSi(CH3)3
OCOCH3

C6H5I(OCOCH3)2
CH2Cl2; 0-20 oC

O
OCOCH3

BF3.(C2H5)2O
20 oC ; CH2Cl2

81%

, .
( (III)
). ArI+-OSO3H
-:
1

Ar I=O + 2H2SO4
1

Ar I-O-SO3H HSO4 + H2O

2

H2SO4

Ar IOSO3H + Ar H 0-5 oC
1

Ar IAr HSO4

NaBF4

Ar IAr BF4 + NaHSO4

: -, - -, -,
- ..
22.1.

1. (C6H5)2I BF4 + NaSCN

2. (C6H5)2I BF4 + NaN3
3. Ar2Br BF4 + NaNO2

100 oC
-

C6H5SCN + C6H5I + NaBF4

80 oC
-

C6H5N3 + C6H5I + NaBF4

60 oC
-

4. (C6H5)2I BF4 + C6H5SO2Na

O
C6H5

97-98%

98%

98%

98%

ArNO2 + ArBr + NaBF4

70-80%

70-80%

20 oC
-

C6H5 + C6H5I + NaBF4

O 99%

1689

99%

1690

CH3

5. (C6H5)2I Cl + C6H5 C
O
C6H5C
81%

C C6H5

0-5 o C
(CH3)3COH

O
C(C6H5)2

+ C6H5I + KCl

CH3

6. (C6H5)2I BF4 + CH2 C CHCOCH3 . NH

3
O

C6H5CH2COCH2COCH3 + C6H5I + NaBF4

92%

OK

7.

80 oC

+ (C6H5)2I Cl

(CH3)3COH

CH3
O
CH3

+ KCl + C6H5I

C6H5

68%

8. (C6H5)2l BF4 + (C2H5)2NH

9.

200 oC

(C6H5)2Br BF4 + N

C6H5N(C2H5)2
88%

C6H5

BF4 + C6H5Br

N
85%

,
.
, ,
.
-
-.

(C6H5)2Br BF4 + C2H5ONa

(C6H5)2I BF4 + C2H5ONa

70 oC
C2H5OH

70 oC
C2H5OH

C6H5OC2H5 + C6H5Br + NaBF4

96-100%

100%

C6H5OC2H5 + C6H6 + C6H5I + NaBF4

14%

1690

68%

92%

1691

(C6H5)2Br BF4 + (CH3)2CHONa

90 oC
(CH3)2CHOH

C6H5OCH(CH3)2 + C6H6 +
92%

4%

+ C6H5Br + (CH3)2CO + NaBF4

100%

4%

(C6H5)2I BF4 + (CH3)2CHONa

90 oC

C6H5OCH(CH3)2 + C6H6 +

(CH3)2CHOH

69%

31%

+ C6H5I + (CH3)2CO + NaBF4

100%

31%

-,,
, ,
, , :

(C6H5)2I . + (CH3)2CH-O .

1) (C6H5)2I + (CH3)2CH-O

C6H5 . + (CH3)2CH-O . + C6H5I

2) C6H5 . + (CH3)2CHOH

C6H6 + (CH3)2C-OH

C6H5 . + C6H5I-C(CH3)2

3) (CH3)2C-OH + (C6H5)2I

OH
4) C6H5-I-C(CH3)2

C6H5I + (CH3)2CO + H

OH
,
+

Ar2Hal

ArHal Nu, SNAr

, .

Ar2Hal + Nu:

SNAr

ArNu + ArHal

, ,
SRN1- -,
- :
:

Ar2Hal + Nu

Ar2Hal + Nu

Ar2Hal .

Ar . + ArHal

Ar . + Nu

ArNu

ArNu + Ar2Hal . ..

ArNu + Ar2Hal2

1691

1692
SRN1

- -, -,
- . . Ar2Hal+
, -
-,
SRN1 -.

22.2.5.
- ,
, ,
.
. ,
,
. ,
.

, .

22.2.5.. -


.

ArN2 Cl + ROH

SN1

ArOR + N2 + HCl

, ,
.
-
.

O
ArN2 + RCH2OH

ArH + RC
H

+ N2 + H

., .
.
:

ArN2 + CH3OH
ArN2

ArN2 + CH3OH

Ar . + N2

1692

1693

.CH2OH

CH3OH

+ H

Ar . + CH3OH

. CH2OH

ArH +

ArN2 . + CH2OH

+ ArN2
CH2OH

HC

.. (HC

OH
H

+ H

Ar . + N2 ..

ArN2 .

. CH2OH

.
,
:

NaNO2;

N2

NO2 H SO ; 0-5 oC
2
4
O2N

CH3

CH3

CH3

NH2

NaNO2;
H2SO4; 0-5 oC

O2N

C2H5OH
80 oC

N2

OC2H5 58%
C2H5OH
80 oC

O2N
70%

. , ,
90% ,
.

C6H5N2

H
C 2H 5O
<
pH 1
C2 H O
5 H
pH>7

C6H5OC2H5
90%

C6H6
100%

,

.

32.

ArN2 Cl + H3PO2 + H2O

0-5 o C
H2O

1693

ArH + H3PO2 + HCl + N2

1694

,
32.
, 30-50%- 32 0-5 24 .
60-80%.
32, -, ,
:
:

Ar . + N2 + H2PO2 .

ArN2 + H2PO2
:

ArH + H2PO2 .

Ar . + H3PO2
ArN2 + H2PO2.

Ar . + N2 + H2PO2

H2PO2 + 2H2O

H3PO3 + H3O

..

1,3--

1,3,5-

I - - II .
.

Cl
O 2N

NO2

N2

NH2
NH3
CHCl3

O 2N

NO2

NO2

O=N-OSO3H
10-20 oC

O 2N

NO2

NO2
O 2N

NO2

NO2

H3PO2
H2O; 0-10 o C

60-65%

NO2

COOH

COOH

Br

Fe + HCl

NO2

Br

NH2

COOH
Br
N2

H3PO2

Br2
HBr; H2O

Br

COOH
Br
NH2
Br

COOH
Br
70-80%

0-5 o C

Br

Br

1694

NaNO2;
HCl; 0-5 oC

1695

CH3O

CH3O

OCH3
NaNO2;
HCl; 0-5 oC

NH2

H2N

OCH3
N 2 Cl

Cl N2
75-80%

CH3O

OCH3

H3PO2

82%

. -,

.

Cl N2

N2 Cl

NaBH4;
; 0 oC

75%

22.2.5.. ( )


, .

ArN=NAr

CuI(NH3)

ArN2

CuI(NH3)

Ar-Ar + N2

,
.

.
1

NaOH
HOH

Ar N2 Cl + Ar H

Ar 1- Ar 2 + N2 + NaCl

1924 .
.
. , 15-30%,
40-60%
.

Br

NaOH
-; 5 oC

N2 Cl +

Br
35-40%

+ NaCl + H2O
- .
,

1695

1696
. ,

(),

-:

ArN2 + ArN=N-O

Ar-N=N-O-N=N-Ar

-, , - -:

ArN2 + 2OH
ArN2 + CH3COO
Ar-N=N-O

Ar-N=N-O

+ H2O

Ar-N=N-OCOCH3
+ (CH3CO)2O

CH3COO

()
- :

Ar-N=N-O . + Ar . + N2

Ar-N=N-O-N=N-Ar

Ar

Ar. +

.
,
:

Ar
H

+ Ar-N=N-O .

Ar-C6H5 + Ar-N=N-OH

Ar-N=N-OH + OH

Ar-N=N-O

+ H2O ..

,
-
- -,
.

Ar
H

+ ArN2

Ar-C6H5 + Ar + N2 + H

-
,
. ,
,
.

( 14).
, -

1696

1697
-
.

N2 + C6H5NO2

NO2

NaOH
H2O; 0-5 oC

- : - : 60 : 10 : 30

. , ,
- - ,

, :

NO2

NO2

NO2

.
H

O N O.

Ar

Ar

Ar

Ar

- ,
-
- -.

- ,

- , ,
( 27).

, ,
.

, Pd(II), Pd(0), Ni(II),

.

C6H5MgBr + Br

Cl

C6H5PdI[P(C6H5)3]2

C6H5

Cl + MgBr2
82%

CH3

CH3
CH3

MgBr + C6H5Br

NiCl2[(C6H5)3P]2
; 0 oC

CH3

CH3

C6H5 + MgBr2
96%

1697

CH3

1698

CH3O

MgBr +
Br

NiCl2[Ph2P(CH2)3PPh2]
; 0 oC

CH3O

+ MgBr2

86%

- g Li-
,
, ,
, (O)R, COOR, NO2, OH, CN .
, -
, , .

n-CH3C6H4ZnCl + n-CNC6H4Br

NiCl2[(C6H5)3P]2
; 2 0 oC

CN + ZnClBr

CH3
90%

ZnCl + I

COOCH3

Pd[(C6H5)3P]4
; 20 oC

COOCH3 + ZnClI

O
83%

- - ,

.

Sn(CH3)3 + I

Z
X

Pd[P(C6H5)3]4 C6H5PdI[PPh3]2
;

80-100%

Z
Z = OCH3; CH3; C6H5; Cl; C6H5 N
X = NO2; CH3CO; COOCH3; Cl; CN
1

Ar2Hg + Ar I

C6H5PdI[PPh 3]; N(C4H9)4I

; 20-70 o C

Ar 1- Ar

60-95%

-
. -
- - -
,
(0) (0).

1698

1699

C6H13C

CH + (i-C4H9)2AlH 0-(-20) oC
Br

C6H13

; Ni(PPh 3)4
o
0-20 C ;

Al(C4H9-i)2

H
C6H13

H
93%

- .
-

(55)2ZrHl:

RC

(C6H5)2Zr HCl
; 0-10 o C

CH

Zr

Cl
(C5H5)2

CH3
H

Br ;

Ni[P(C6H5)3]4
0 oC ;

H
H
H

CH3

, - (,)

99%.

.
-
g. Al, Zn, Sn, Zr, B

(II)

(0),

NiCl2[(C6H5)2PCH2CH2P(C6H5)2];

NiCl2[(C6H5)2P(CH3)3P(C6H5)2]; Pd[(C6H5)3P]4

C6H5MgBr +

Cl

Cl

C6H5
H

C6H5
90%

NiCl2[(C6H5)2PCH2CH2P(C6H5)2]
; 20 o C

C6H5

+
C6H5

1699

10%

1700

R
Cl

MgBr +

Pd[P(C6H5)3]4
; 20 oC

R
R

Cl + MgBrI

80-90%

1968 .

:

RMg + PdX2
[RPdX] + CH2=CH

[RPdX] + MX

[RCH2-CH-Y]

RCH=CHY + HX + Pd

PdX

M = Li; Mg; Hg; Sn; Si

, ,
- .

R-Pd. d,
Pd(0) .
RPdX

ArBr + Pd

ArPdBr

ArI + Pd

ArPdI

, ,
,
:
Pd(OAc)2; P(C6H4CH3-o)3

+ CH2=CHY ; 100-150 oC

CH CHY
Z

50-98%

Z = COOCH3; CN; CHO; Cl; F; CH3

Y = CN; COOCH3; H; CH3; Cn C2n+1 ; Ar

- ,
, -(-) .
:

N N BF4
+

CH CH2

Pd(OAc)2; CH3COONa
20 oC ;
CH2=CH2
72%

1700

1701

22.2.5..
, 1939 .,
, ,
.
Cu2Cl2

ArN2 Cl + CH2=CHX

ArCH2CHX + N2
Cl

X = CN; COOR

-
.
-
.

N N BF4
+

CH CH2

Pd(OAc)2; CH3COONa
20 o C ;
CH2=CH2
72%

22.2.5..
(II)
.

O
ArN2 BF4

+ CO + CH3COONa

(CH3COO)2Pd
30 ; 25-30 o C

Ar-C-O-C-CH3

100
.
o
ArCOOCOCH3 100-120 C

(CH3CO)2O + (ArCO)2O

(80-90%)

.

22.2.3.

,

. ,
,
. -

.
.
1). .

1701

1702
,
N=N.

Ar-N=N

ArN2 +

X = OH; NH2

- (ArN2+) - (ArX) .
,
,
.
,
.
,
. X = O- > NR2 >
NHR > NH2 ~ OR >> CH3 (Alk). , + +I O-, +
.

- .
.

. ,
.
1- 4-
,
, 4--. , , -
, 2,4-
, 2,4,6-
.
,
, .
-
. 8-10,
. ,
. -

--, -,
, , , .
, 12
ArN2+ ArN=N-O-.
e 8

1702

1703
10. , 3-5, ,
.

. -
- .
-, , 1-2%.
, - , -. - , ,
, .
4, 2.
. ,

-,

. - , - -, .
- -,
-,
.
, ,
. , , 4--5-2,7- (-)
3, 6.

OH NH2

O3S

OH NH2
+ N2
SO3

NO2

N=N

pH~3
H2O

O3S

NO2

SO3

OH NH2
N2
H2O; pH~10

N N

N=N

O3S

SO3

NO2

. - , .
(, , , .).
-,
.

1703

1704

CH3
CH3

N2 +
NaO3S

CH3

N=N

SO3Na

R-

2R

SO3Na
OH

SO3Na

SO3Na

OH

+
NaO3S

SO3Na

OH

CH3

OH

NaO3S

N=N

N2
SO3Na

SO3Na

R-

SO3Na
H2N

N2 + HO

H2N

N=N
HO

HO

SO3Na

HO
SO3Na

4BS

NH2 OH

OH NH2
+

N2

N2

SO3Na

NaO3S

+
SO3Na

NaO3S
OH NH2

NH2 OH

NaO3S

SO3Na

N=N

N=N

SO3Na

NaO3S

SO3Na

22.2.4.
ArN2+ ,
- .
. . ,
. ,
( ) ,

1704

1705
. ,
-.
(.. 3).
, - (k2)
(. 13.5).
1

ArH + Ar N N
-

k1
k- 1

Ar

k 2 [B]
1

N=N-Ar

(2)

ArN=NAr 1 + BH

(1)

(. 3, 3.3.6.a) -,
.

k =

k1 k 2
k 1 + k 2 [ B ]

(k-1<<k2[B]), [B] , k
= k1. k-1..k2[B], [B] . k1k2[B],

.
, ,
H/D H/T. 13.5.
k-1/k2[B] (1) (2),

.

I-III.

SO3

O
O

O3S
SO3

4--1

SO3
II

7--1,3

III

4--2

( -).
I
; -.
II .
III I II
, ( 13.5).
, 3 ,
, 1. -

1705

1706
3/1- 1,3- III
, III.
3, k2 - , - ArN=N-,
, 2 4.

.
,
.
(). , ,
.
- ,

-
, ,
, .
k1

ArN2 + H2N

k- 1

k2

ArN=N
H

Ar-N=N-NH2
+

- H+
NH2

Ar-N=N-NH

ArN=N

NH2 + BH

k- >> k1 > k2
1

, , ,

. ,
,
.
-
.
- ,
.
-
.

1706

1707

k1

ArN2 +

Ar-N=N-O

k- 1

k2

ArN=N
H

ArN=N

OH

k- >> k1 > k2
1

22.2.5.
, ,
,
.
.
. 1875 .
. ,
-N-N'-,
:

ArN2 X

Na2SO3;
H2O; 0 o C

ArN=N-SO3Na

NaHSO3
H2O

H
ArN-N-SO3Na
SO3Na

HCl
H2O t oC

ArNH-NH2.HCl

. (1883 )
.

ArN2 Cl + 2SnCl2 + 4HCl

0-10 oC

ArNH-NH2.HCl + 2SnCl4

22.2.6. ,

, ,
.
. ,
, ,
:

Cl

N2 Cl + SCN

NCS

1707

N2 Cl

1708

NO2
N2

Cl

NO2
H2O

N2

OH

:
Cl

NO2

NO2
NH2

N2 Cl

NaNO2;
HCl; 0 o C

NO2

NO2
H2N

N2 Cl

H2O
HCl; 5 oC

NaNO2; H2SO4
H2O; 20 o C

N2

OH

22.2.7. ()

R2C=N=N .

R2C N N

.
,
, .
.

,
.
-20o .
, .
-20o
.

Ar2C=N=N

1708

1709

22.2.7..
,

1930

N-

O
H2N

C N

CH3

+ OH

0-5 oC

N=O

O
CH2N2 + H2O + H2NC

N-

N-

.

N- .

N O
RCH2

R CH N N O Y

B = OH; Y = C

O
OC2H5

R CH=N=N + OY

; CH3C O; p-CH3C6H4SO2

.
Y .
YO-.

CH2=N=N

N--N-

- 0-5.
0-(-20).

CH3

N C

NH2

KOH;
-; 0 oC

CH2=N=N

+ NH3 + K2CO3 + H2O

O
, -, . .
,
:

O
CH3

CH3

C NH2 + OH

C NH2

O N OH

O N O

1709

1710

O
CH3

C NH2

CH3-N=N-O

+ HO-C-NH2

H2O

O N OH

CH3-N=N-OH

CO2 + NH3

CH3-N=N-OH + OH

CH2-N=N-OH

CH2=N=N + OH

..
HgO

R2C=N-NH2

R2C=N=N

,
(. 24).
.

+ 2CH2N2 0 oC
Cl

O
CH=N=N

+ CHCl3 + N2

Cl

O
R CH -N N
2
Cl

+ CH2N2

CH2N N + Cl
CH2N2 + HCl

O
CH=N=N

+ HCl

CH3Cl + N2

- :

CH2N N + Cl

O
CH2Cl + N2

1,3- 1,3-

n-CH3C6H4SO2N=N=N

.
1

R COCH2COR + n-CH3C6H4SO2N3
N=N
1

NaOH; NR4 Cl
CH2Cl2-H2O

R CO-C-COR + n-CH3C6H4SO2ONa
80-95%

1710

1711
, ,
COR; COOR; NO2; CN).
-:

H2NCHCOOC2H5 + NaNO2 + HCl

H2O
0-5 oC

N=N=CH-COOC2H5 + NaCl + H2O

. 21,

.

SN2, "" SN1.
1

R1 CHNHNH2 + HNO2
R2

R CH=N=N
R2

X
1

N2 + R CHX

S N2

SolOH
S N1

R R2CHOSol

R CH + N2
R2

22.2.7..

, ,
-10-20.

RCOOH + CH2N2

-10 oC

ArOH + CH2N2 ;o BF3

-10 C

ROH + CH2N2

; 0 o C
(2H5)2O.BF3

RCOOCH3 + N2
ArOCH3 + N2
ROCH3 + N2

,
H3N2+,
.

RCOOH + CH2=N=N

[RCOO CH3N2 ]

RCOOCH3 + N2

.
.
5.
,

1711

1712
.
-, 18.

RCOCl

CH2N2

Ag

RCOCH2N2 h

[R-CH=C=O]

H2O

RCH2COOH

26.

.
. . SN2-
,
R.

O
R

CH2 N N
+ CH2=N=N

C O

R
CH2
N2 +

R C
O
R

O
C CH2 + N2

O
RCH2CR + N2

,
. , -
, .
30-75%,
.
, ,

.
, 20-30%, .

. ,
- .
,

1712

1713

.
CH N

O +

2 2
O -

CH2
15%

63%

CH N

2 2
O -AlBr3

60%

0-20 oC

. C8-C12
, ,
.
1,3 .
25.

22.3. -
XIX
-

H2C

CH2=N=N (.)

N
N (.). .

- .

,
, . 1961

R2C

N
N . -

.
1

NH
NH

HgO Ag2O

R1; R = Alk

R1
2

N
N

+ H2O

40-90%

3,3-
-O-.

1713

1714

R COR + 3NH3 + NH2OSO3H

1

NH

+ H2O + (NH4)2SO4

NH

o ,
.
20 100.
1-.
1

N
N

0 oC

+ R MgBr

N MgBr H2O
C
3
0 oC
N R

NH
N

50-95%

,
N-.

R2C=N2

1) (CH3)3CMgCl
2) H2O

R2C=N-N

C(CH3)3
H

, ,
(. 5).

20 . , ,
. ,
15N,
. ,

.

H2C

N
N

h
20 K; N2

CH2 + N2

CH2=N=N

22.4.
RN3, ,
,

R-N-N N

R-N=N=N

-
.

1714

1715

22.4.1.

.

.
.

C6H5CH2CH2Br + NaN3

20 oC

C6H5CH2CH2N3 + NaBr
86%

18--6

H3(CHC2)14CH2Br + NaN3

H3CN; 20 oC

CH3(CH2)14CH2N3 + NaBr
90%

18--6

Br + NaN3

N3 + NaBr

H3CN; 20o C

54%

,

(. 18).
CH3CN
CH2Cl2

RCOCl + NR4 N3

RCON3 + NR4 Cl
60-90%

.
c-
( 5).
-H O

RCH=CH2 + Hg(N3)2 CH2 OH

3
NaBH4
-H2O

R-CHCH2-HgN3
N3

R-CH-CH3
N3

-.

RCH(COOC2H5)2 NaH
RCH(COOC2H5)2
; -30 oC

n-CH3C6H4SO3Na
; -30 oC

R-C(COOC2H5)2
N3

ArN2 Cl + NaN3

H2O

1715

ArN3 + NaCl + N2

1716

ArNHNH2 + HNO2

H2O-C2H5OH

[Ar-NH-NH-N=O] + H2O

Ar-N=N=N + 2H2O

.

ArN2 Br + 4NH3

ArN3 + 3NH4Br

SNAr.

NO2

NO2
O2N

18--6;

Cl + NaN3 CH CN; 25 oC O2N

3

N3 + NaCl

22.4.2.
> >
> .
,
.

22.4.2..

, , .
.
.
H CN;

Br N(C3 H ) N
4 9 4 3

N3

LiAlH4

NH2
54%

CH3(CH2)14CH2Br H3CN;

N(C4H9)4 N3

CH3(CH2)14CH2N3

LiAlH4

CH3(CH2)14CH2NH2
78%

.
.

C6H5CH=CH-CH2N3 + H2

Pd/BaSO4

C6H5CH=CHCH2NH2
93%

,

.

1716

1717

H
C

R
H

+ IN3

CH2Cl2

N3

C H
I

H C
R

NH
R
C C
R
H

LiAlH4

,
. 18
.

22.4.2.. 1,3-

1,3-,
( 25).
, , , . [4+2]-
1,2,3-2-.

C6H5

C6H5CH=CH2 + C6H5N3

C6H5 CH

100 C

C6H5

CH2

- N2

CH3

C6H5

CH3OOC-CH=CH2 + C6H5N3

CH2

C6H5

C N C6H5
o

90 C

CH COOCH3

N
CH2

CHCOOCH3 + N2

95%

1,2,3-2- 90-100
. ,
.

OCH3 SO2Ar
N
100 oC
N
-N2
N
H

OCH3
+ ArSO2N3

H2O
+

COOH

OCH3
C
NSO2Ar

87%

1,3- [4+2]-
1,2,3-.

HC

C COOCH3 +

N3

N
67%

1717

N
COOCH3

1718

N C6H5
N 88%
N

+ C6H5N3

RN, .

RN RN . e ,
100-150 .
.

. , , , , ..
- -.
:
1

RN +

C C

R2

C
N
R

R2
H

:N-COOC2H5 .

+ N 3COOC2H5

t oC

N COOC2H5 + N 2
50%

O
N

N3 +

h -78oC
CH2=CH-COOCH3
CH2Cl2

O
C
NH
NH
C
O

NH2
N
NH2NH2.H2O
CH
2 CH COOCH3 +
CH3OH

N N

CH2
CHCOOCH3

. ,
- sp3- .
, , - >
> .
.

1718

1719

CH2
H
N3

C*

CH3

t oC

C2H5

CH2
C*
NH

CH3
C2H5

180 oC

+ N2
N
H

N3

1719

+ N2

78%

1720

23

1. ..................................................................................................................................... 1720
1.1. ................................................................................................................................ 1720

2. ....................................................................................................... 1722
2.1. ........................................................................ 1722
2.2. .................................................................................. 1724
2.3. ........................................................................... 1726
2.4. ............................................................. 1727

3. ........................................................................................................... 1730
3.1. .......................................................................................... 1730
3.2. ........................................................................................................... 1733
3.3. - - - .................................................. 1737
3.4. ...................................................................................................... 1740
3.5. .............................. 1741
.......................................................................................................................................... 1741
3.5.1. .............................................................................................. 1741
................................................................................................................ 1743
3.5.3. ................................................................................................. 1745
3.5.4. .............................................................................................. 1746
3.5.5. -................................ 1747
3.5.6. .............................................................................................. 1752
3.5.7. ....................................................... 1755
3.5.8. - - .............................................. 1758
3.5.9. .................................................................................................................. 1760
3.6. .................................................... 1760
3.7. ............................................................................................................. 1763

4. ..................................................................................................................................... 1769
4.1. ............................................................................................................ 1771
4.2. ........................................................................................ 1773
.......................................................................................................... 1773
4.2.2. ............................................................................. 1777
4.2.3. ,- ....................................................................... 1778
4.2.4. ................................................ 1780

1.
1.1.

,
. ,

, , , .., :

1720

1721

OH

OH

l
4-

OH

1-

2-
HO

OH

9-

9-

- . , .
1825 ,
, .
,
65, 65,
.
.
OH

OH

OH
NO2
F

C2 H5
4-

3-

2-

. ( ),
:
OH

OH

OH

CH3
CH3

2-,
-,
(-)

3-,
-,
(-)

CH3
4-,
-,
(-)

,
.

1721

1722

OH

OH

CH3

CH(CH3 )2
CH3

(CH3 )2 CH
5--2-
()

2--5-
()

OH

OH
OH3

OH3
CH2CH=CH2

2-,
()

4--2-,
()

.
OH

OH

OH

OH

OH
1,2-,
-,
()
OH

OH
1,4-,
-,
()

1,3-,
-,
()
OH

OH

OH

OH

OH
1,2,3-
()

OH

HO

OH

1,3,5-
()

1,2,4-

2.
2.1.

300350.

1722

1723
o

ArSO3Na + 2 NaOH

300-350 C

ArONa + Na2SO3 + H2O

ArOH + NaCl

ArONa + HCl

.
,

- , - -
.
HO

SO3
OH

OH

SO3

O
+

OH

SO3

+ SO3 + H2O

,
I-14C, ,
, .

. 4 -.
SO3Na

ONa
72% NaOH - 28% KOH; 330 C

+ Na2SO3 + H2O

CH3

CH3

, 2- ,
, .
SO3Na

SO3Na

ONa

NaOH; 325 C

NaOH; 340 Co

ONa

ONa

SO3Na

1723

1724

SO3Na

ONa

ONa

1).NaOH; KClO3;200 C
2).H3O

(1,2-)

-
. -, .
NaO3S

HO

NH2

NH2

NaO3S

SO3Na

1)NaOH; 180 C
2) H2SO4; H2O

NaO3S

SO3Na

8--1--3,6
(-)
NaO3S

HO
NH2

NH2

1)NaOH; 180 C
2) H2SO4; H2O

NaO3S

NaO3S
6--4-2-
(-)

2.2.

. 1520%- 360-390 28
(280-300)

-I14C ,

-,

1724

1725

- 2 4-.
Cl

NaOH;360 C
H2O

C6H5O
H2O

C6H5O
H2O
C6H5

OH
H2O

H2O

C6H5

-,

OH
H2O

C6H5

-,

,
- - .
, 2--

4-

-. 360390 NaOH . 2- 4-
,
20-25%. ,
- .

- -
3:2 -, 1- 2- 1, 2-. (II),
, -

SNAr-.

(II)
- .
o

CH3

Cl+

2 NaOH

CuSO4;190-200 C

1725

CH3

ONa+

NaCl + H2O

1726

Cl

ONa

CuSO4;190 C
H2O

Cl

+ 4 NaOH

Cl

+ 4 NaOH CuSO4;175 C

ONa

+ 2 NaCl + 2 H2O

Cl

ONa+

NaO

H2O

2 NaCl + 2 H2O

- -
.
SNAr , -
.
Cl+

NO2

o
2 NaOH 160 C

ONa+

O2N

NaCl + H2O

76%
NO2
Br+

NO2

2 NaOH

NO2

NO2

0-20 oC

ONa+

O2N

H2O

NaBr + H2O

NO2

97%

.
Cl

NC

CN

NC

CN

CN

50 C

+ H2O

NC

CN

NC

CN

+ HCl

CN

2.3.

1726

1727

1.HNO2 ;

ArNH2

2.H2 SO4 ;H2 O

ArN N HSO 4

H2 O;100 C

ArOH + N 2 + H2SO4

H2 SO4 ;H2 O

, SN1,
.
15.

.
:
N N HSO4

+ H2O

OH

H2 SO4 ;H2 O;100 C

+ N2 + H2SO4

NO2

NO2
81-86%

N N HSO4
OCH3

OH

H2 SO4 ;H2 O;100 C

OCH3

+ N2 + H2SO4

8O-90%
N N HSO4

OH

H2 SO4 ;H2 O;100 C

(CH3 )3 C

+ N2 + H2SO4
(CH3 )3 C

C(CH3 )3

C(CH3 )3
80%

N N HSO4

OH

H2 SO4 ;H2 O; 80 C

+ N2 + H2SO4

Br

Br
78%

2.4.

- .
-
-.
1727

1728

C(CH3 )2

H3 PO4 ;250 C;25

+ CH3CH=CH2

100-130
.
CH3
C O-OH

CH3

C(CH3 )2

100-130 C

+ O2

,
.

.
,
.
CH(CH3)2

+ X

C(CH3)2

C(CH3)2

CH3
C-O-O
CH3

+ O-O

CH3
C-O-O

CH3
H C

CH3

CH3

CH3
C-O-OH

+ HX

CH3

CH3
C

..

CH3

, ,

-. ,
.
CH3
C-O-OH
CH3

CH3
C-O-OH2
CH3

1728

O-C-CH3
CH3

H2O

1729

CH3
O-C-OH
CH3

CH3
O C-OH
H CH3

+ H

O
OH + CH3-C-CH3 + H

1% 50-90.
C(CH3)2OOH

OH

1%- H2SO4;50-90 C
H2O

+ CH3C(O)CH3
90%

- .
- - -

, .
.
CH3
CH3 C O-O-H

CH(CH3)2

O2;100-130 C
CH(CH3)2

OH
H3O

CH3
C O-O-H
CH3

+ CH3C(O)CH3
OH

,
.
-
, (II) (III).
22 (II)
.
Fe2+ + HO-OH Fe3+ + OH- + HO.

.
(III) ,
1,11-4,41--4,41-,
.
1729

1730

OH

HO

Fe

OH

3+

HO

OH + H

OH
+ 2H2O

(II)
, , (II)
-, (III)
. ,

.

.

.
+ HO-OH

FSO3H

OH
56%

CH3

CH3

+ CF3COOOH
CH3

BF3 (C2H5)2O

CH3

OH

CF3COOH
CH3

CH3
80%

3.
3.1.

, .

1730

25

(10,00),

1731

(18,00). ,
.
OH
O

+ H2O
OH

+ H3O

pKa=10.00

+ H3O

pKa=18.00

+ H2O

,

G .
-
ROH
RO.
RO , ROH,
, . ,
,
, , .. .
,
108 - .
+ -.
-
-
-. -
, ..
- -
. -, ,
,
- - (.
23.3.2).
- -
-

1731

1732

- .
-
, -, , ,
.
,
. , ,
,
.

. 23.1
25.
23.1.

-, - - 25

10.00

10.00

10.00

CH3

10.29

10.09

10.26

C(CH3)3

10.62

10.12

10.23

C6H5

10.01

9.64

9.55

OCH3

9.98

9.65

10.21

COOC2H5

9.92

9.10

8.34

8.73

9.29

9.89

Cl

8.56

9.12

9.41

Br

8.45

9.03

9.37

8.51

9.03

9.33

HCO

8.37

8.98

7.61

CN

6.86

8.61

7.97

NO2

7.23

8.36

7.15

5.26

5.5

1732

1733

1-

9.39

2-

9.63

2,4-

4.07

2,4,6-

0.42

(1,2-)

9.34 12.6

(1,3-)

9.32 11.1

(1,4-)

9.85 11.4

3.2.

, -
.

- (2,4- 2,5-)

, ,
- .
OH

H H

H
H

Ho=+23/

+23 /,
9,5 2,5, ..
. ,
, ,
- ( 17). ,
. -

, 1-

12,5

9-

1733

1734

Ho=+12.5 K/

OH

O
Ho= -1.4 K/

9- ,

( , , l4)
(20=400 ). -
. , 1,4

10%-

150 C
OH
90%

H
H
H
H
10%

-
(1,3,5-), .

-
. 1968
..
-
- .
-
, - . 1-, 2-
, -
, .

1734

1735

O AlCl3

O-AlCl3

AlCl3,CH2Cl2,20 C
H

OH AlCl ,CH Cl ,20oC

3
2 2

OH

O AlBr3

O AlBr3

O-AlBr3

O-AlBr3

AlBr3,CH2Br2
CH3

CH3

CH3
H

CH3

CH3

CH3

, ..
,
. ,
. , 2-

.
H

O-AlCl3

20 C

90%

C6H6

- AlCl3.
O-AlCl3

O
o

+
CH3

20 C
C6H6

CH3

54%

-
, 1- 2,

- -, 6- 8-

, ,

1735

1736

130150.
OH

NH2

150 C,H2O,8

+ NH4HSO3 + NH3

95%

, . 1904 ,
,
,
.
CH3

OH

NH2

NH
NaHSO3

+
SO3H

NH2

CH3

130 C,H2O,30

SO3H

NH2
65%

+ NH3 + SO2

160 C,H2O,12

OH

90%
NH2

,
-
:
HO

OH

HO

HO
OH
o
NH3,SO2,40 C

NH3,SO2,20 C
NH2

H2O,5

OH

H2O,24

NH2

NH2

82%

100%

, ,
- - - -
- ,
.

1736

1737

OH

O
H

SO3NH4

H
H2N

HN

OHH
H
SO3NH4
H H

-H2O
H

H
H
SO3NH4
H H

NH3

H
H
SO3NH4
H H

NH2

+ NH3 + SO2 + H2O

. 1- 2--
130-150
, :
HO3S

NH2

110-120 C,H2O

+ H2O + NaHSO3
SO3H

HO3S

OH

96%

SO3H

-
:
COOH
H2N

NH2

NH2

o
100 C

HO

H2O

OH

OH

45-53%

3.3. - - -

-, ,
- -. -
-
.

1737

1738

.
ONa

CH3

20 C,

+ (CH3O)2SO2

96%
ONa

OCH2(CH2)3CH3

60 C,

+ CH3(CH2)3CH2Br

80%
NO2

NO2
ONa

OCH2COOC2H5

+ BrCH2COOC2H5

65 C,

87%

- 2,4-
2,4- ,
.
ONa
Cl

OCH2COOH
Cl

+ BrCH2COOH

Cl

Cl

-, -.
-
, , .
- -
, (.
, 1963 .).
ONa

CH3OH

+ CH2=CHCH2Cl
H2O

OCH2CH=CH2
100%
OCH2CH=CH2

CH2CH=CH2

+
49%

1738

OH

51%

1739

ONa

+ BrCH2C6H5

CH2C6H5
OH

OCH2C6H5

CF3CH2OH

+
85%

7%

- -
.

. ,
2-,
.
ONa

OCH2CH=CH2
CH2=CHCH2Cl

OH
CH2=CHCH2Br

CH2CH=CH2

C6H6

-
- .
OAl(OC6H5)2

+ (CH3)2C=CH2
OH
C(CH3)3

100 C,17,,C6H5OH

OH

(CH3)3C

C(CH3)3

OH

(CH3)3C

C(CH3)3

+
C(CH3)3

- ,
-
.
(CH3)3C

ONa

C(CH3)3

+ C6H5CH2Br

(CH3)3C

OCH2C6H5
C(CH3)3 (CH3)3C
+

C6H6

17%

1739

34%

C(CH3)3
CH3

1740

ONa

(CH3)3C

(CH3)3C

C(CH3)3

+ CH3I

C(CH3)3

C6H6

C(CH3)3

C(CH3)3

80%

.
OH

OH3

-N2

+ CH2=N=N

3.4.

.
,
.
o

CH3COOH + C6H5OH

CH3COOC6H5 + H2O + H =+1.5K/

CH3COOH + C2H5OH

CH3COOC2H5 + H2O + H =-4.6 K/

Na-, K- .
OH

OC(O)CH3

H2SO4
60 oC

+ (CH3CO)2O

96-98%

OH

OC(O)CH3

ONa

+ (CH3)3C(O)Cl

OC(O)C(CH3)3

NO2

NO2

OH

+ (CH3CO)2O

H2SO4,60 C

COOH

OC(O)CH3
COOH

1740

1741

3.5.

- .
,
.
,
.

3.5.1.

(FeCl3, FeBr3,
AlCl3 .) .

-. -
-
- , .
, ,
,
- -.
O

Br2,5 C,H2O

O Br ,H O
2 2

-HBr

Br

Br

Br
O

Br

H
Br

- HBr

Br

Br
H

Br

Br
Br

OH

+ 3HBr

Br
Br

Br

Br2,H2O

Br

Br

2,4,6.

105 . 2,4,61741

1742

2,4,4,6--2,5-, .
Br

Br

OH

Br

+ Br2

Br

Br
Br

+ HBr

Br

2,4,6.
2,6-- 2,4,6-
.
(CH3)3C

OH

C(CH3)3

+ Br2

(CH3)3C
CH3COOH
Br

C(CH3)3

+ HBr

C(CH3)3

C(CH3)3

(CH3)3C

OH

C(CH3)3

+ Br2

CH3COOH

(CH3)3C

C(CH3)3

+ HBr

Br

.
- 2,4-.
OH
o

+ Br2

OH

HBr,H2O,5 C

+ HBr
Br

OH
o

+ 2Br2

81%

OH
Br

HBr,H2O,40 C
Br

+ 2HBr

87%

,
-.

1742

1743

,
.
OH

OH

CS2,0 C

+ Br2

+ HBr
Br

OH

80-84%
OH

OH

Cl

CCl4,0 C

+ Cl2

+
Cl

26%

74%

, ,
(II).
OH

OH

Br2 O

CHCl3,0-20 C

88%

Br
OH

CuCl2

OH

,20 C
83%

/-
, .

20-25%-
- -.
OH

OH

OH
o

20% HNO3,,25 C

+
NO2
15%

1743

35%

NO2

1744

,
-. -
:
O-H

O
N

2,4,6-

( )
.

4--1,3-

, .
OH

OH

SO3H

.H2SO4,100 C

HNO3,0 C

SO3H
O2N

OH
SO3H

O2N

HNO3,100 C

SO3H

OH
NO2
70%

NO2

-
.

(- )
,
.

N2O4,
- .
OH
o

HNO3,CH3COOH,25 C

OH

NO2
70%

1744

1745

OH
o

OH

N2O4,CH2Cl2,0 C

OH
NO2

NO2

+
NO2

3.5.3.

- - . 20
49% - 51% -,
120 - 96%.
OH

OH

SO3H

20 C
+

OH
SO3H

98%- H2SO4

51%
OH

OH

SO3H

120 C

SO3H

49%

96%

4%

,
- ( . . 13).
- ,
-, .

2-.

1745

1746

SO3H
OH

98%- H2SO4
-10 oC

ClSO3H
-10 oC

OH

92%- H2SO4
100 oC

HO3S

SO3H

OH

OH

92%- H2SO4
100 oC

92%- H2SO4
120-130 oC

OH
HO 3S

SO 3H

2- 98%- -10

2--1-,

2- 92%- 90-100
6--2- 7-1-. 120-130

6--2-

-2,7-

(R-)

3-

2-.

3.5.4.

,
.
-
. - -
.
OH

OH

OH

N=O

NaNO2,HCl,H2O,0-5 C

+
N=O
1

1746

15

1747

,
.
OH

OH
HNO2

NH2OH

N-OH

N=O

n-
.
, .
OH

N-OH

OH

NH2OH

25%-
HNO3

NO2

N-OH

N-OH

N=O

- ,
.
OH

OCOCH3
(CH3CO)2O

N=O

O
t oC

+
N=O

OCOCH3

N-OCOCH3

N=O

3.5.5. -

: ,
.
ArOAlCl2,

, -2,
. ,

1747

1748

- 2,6---4-

(),

.
OH

OH
o

(CH3)2C=CH2,-2,100 C

(CH3)3C
CH3

CH3

C(CH3)3

2,4,6-

.
OH

OH
o

(CH3)2CH

(CH3)2CHOH,HF,0-8 C

CH(CH3)2
CH(CH3)2

95%

-,
- -.
,

OH

OH
AlCl3 ,HCl, 100 oC

OH
+
CH3

CH3

CH3

20%

80%

,
.
,
.
- .
, ,
BF3 - 95%- .

1748

1749

OH

OH
o

CH3COOH BF3,20 C
95%

C(O)CH3

. . 1908 ,

AlCl3

AlBr3

- -.
, - -
-.
OC(O)C2H5

OH

OH

1.AlCl3,C6H5NO2,140 C

C(O)C2H5

2.H2O,HCl

35%

C(O)C2H5 50%

- -
. -,
20-25 - -.
OH
o

AlCl3,C6H5NO2,25 C
OC(O)CH3

CH3

CH3

C(O)CH3
OH

C(O)CH3

AlCl3,6H5NO2,165 C
CH3

. () 5-2- , - - 3-4- .
CH3C
COOH

1) AlCl3; C6H5NO2; 25 o C
2) HCl; H2O; 20 oC

OCOCH3

O
COOH
OH

1749

83%

1750

CH3C
CH3COO

COOH

1) AlCl3; 180 o C
2) HCl; H2O; 0 o C

HO

COOH

-,

- -
AlCl3
.
OC(O)CH3

OC(O)CH3

+ CH3C(O)OC6H6

AlCl3

+ C6H5OH
C(O)CH3

.
OC(O)CH3

OH

OC(O)CH3

+ C6H5OH

+
C(O)CH3

C(O)CH3

-
-.

0 AlCl3 AlBr3.
OR1

O
+ R2- C

OR1
o

AlCl3,CH2Cl2,0-5 C

Cl
C(O)R2

85-95%

)

( . , 1915 ).

1750

1751

OH

OH
ZnCl2 + HCl

+ CH3CN

, 0 C

OH

HO

OH

CH3

OH

74-85%

OH

OH

+ C6H5CH2CN

ZnCl2 + HCl

NH2 Cl
C CH2C6H5

, 0 C

OH
OH
C

H2O;
100 oC

C CH3
H2O;
100 oC
OH

C
HO

HO

NH2 Cl

OH

O
CH2C6H5

OH

60-70%

, ArOC(R)=N+H2 Cl-.

(., 1874 )
-.

, .

OH

OH

+
C

OH

H2SO4,120 C
C

O
C

O
( )

9
.

1751

1752

OH

OH

HO
C

O
C

O
C

-
, .
OH

OH

OH

H2SO4

OH
O
C

3.5.6.

( -, - .)
. 13.
- -
. - .
(1876 ).
,

.

50-70.

30%,

. -
-, -,
-.

1752

1753

OH

OH

+ CHCl3 + NaOH

OH

CHCl3,H2O,60 C

+
CHO

OH

CH3

OH

+ CHCl3 + NaOH

CHO

CH3
+

CHCl3,H2O,60 C

20%

10%

OH

CH3

CHO
8%

CHO

20%
CHO

OH

OH

CHCl3,H2O,60 C

+ CHCl3 + NaOH

38-40%
CHO

+ CHCl3 + NaOH

NH

CHCl3,H2O,60 C
NH

31%

:CCl2

-,
. -
:
HO

CHCl3

H2O + CCl3

OH

HOH

CHCl2

O
CHCl2

CHCl2

HO

CHCl

CHCl

HO

O H
CH

+ HO

+ Cl

Cl

O
CHCl

H
CCl2

+ CCl2
O

H2O + CCl2 + Cl

O
HO

Cl

1753

CHO

+ H2O + Cl

1754

D2O 97%
. ,
O

OH

CHCl2

HOH

CCl2

1,2-

-,
. -,
- - ,

, . , ,
-

2--5-

4--4-

-2,5- .
OH

OH
NaOH,CHCl3,60 C

CH3

CHCl3,H2O
CH3

CH3

25%

2,4,6-

CHO
+

CHCl2
26%

, CHCl2 -
:
OH

O
CH3

CH3

NaOH,CHCl3,60 C

CH3

CH3 +

CHCl3,H2O
CH3

CHCl2

O
CH3

CH3

CH3
77%

CH3

CHCl2

2,6----4- ,
, .

1754

1755

OH

O
C(CH3)3

(CH3)3C
CH3

NaOH,CHCl3,60 C
CHCl3,H2O

C(CH3)3

(CH3)3C
CH3

CHCl2
78%

,
,
.
,
.
- ,
CO NaCl.
:CCl2 + H2O

[HO-CHCl2]

NaOH

CO + 2NaCl + 2H2O

, ,
-,
.
O

CCl2

O-CCl2 H O
2

O-CHCl2

NaOH
H2O

+ HCOO

3.5.7.

,
- , . 1909
.

, ,
, ,
..

1755

1756

CH2
CH2
OH

+ nHCHO

CH2

HO

NaOH,H2O,20-150 C

CH2

CH2

OH

OH
CH2

CH2

HO

CH2

CH2

-
,
-

-,

.
O

NaOH,H2O

+ HCHO

CH2O

CH2O

OH

OH

CH2OH

HOH2C

, - -

. , -
- , - -.
O
CH2

OH

to

CH2

O
t

CH2

+ HO

O
+ HO
CH2

OH

-
,-
.

1756

1757

O
CH2

CH2

CH2

HO

- -
-
- . ,
-.

.
OH

CH3
C

+ CH3COCH3

CH3

HO

OH

.

, , ,
:
CH3
2 CH2 CH CH2Cl

CH3

CH3
C
CH3

CH2 CH CH2 O

O CH2 CH2 CH
O

O
CH3
C
CH3

CH2 CH CH2 O

CH3

CH3

CH3

O CH2 CH2 CH2 O

O

CH3

..

1757

1758

3.5.8. - -

. 1860 .
2 150-180 5 ,
.

.
ONa

OH

+ CO2

COONa

180 C,5

OK

OH
o

+ CO2

200-220 C,5
COOK

Na- -

CO2
. , ,

.
ONa

O Na

COONa

+ CO2

OH

, ,
- -
.
-

, ,
, , -.
,
, .

1758

1759

200220 -- -Rb- - .
OH

OH

OK

COOK

200-220 C

+ CO2

+
COOK

- :
O
COOK
2

OK

220-250 C

2
COOK

-
:
OH

ONa

290 C

OH
COONa
+

+ CO2

COONa

,

.
2-:
ONa

+ CO2
OK

+ CO2

260 oC;
5

250 oC;
5
KOOC

OH
COONa
OH

,
. ,
2 50
2,4- .

1759

1760

OK

OH

1.CO2,H2O,50 C
OK

2.HCl,H2O

COOH
57-60%

HO

- -
,
.
ONa

OH
NaHCO3

COONa

H2O

NH2

NH2

3.5.9.

. ,
22.
2R,
- R-.
CH3

CH3
N N
N N
CH3

OH
+

SO3Na

NaO3S

CH3

OH

pH~10
H2O

R-

SO3Na

NaO3S

2R

3.6.

1912

26. 200-220
-, .. .

1760

1761

OCH2CH=CH2

OH

CH2CH=CH2

200-220 C

73%

- ,
-:
CH3

OCH2CH=CH2
CH3
o
CH3
200-220 C

OH
CH3
CH2CH=CH2

..

- .
OCH2CH=CHCH3

OH

CH2CH=CH2

200 C

CH3

,
.

- ,
.
-.
.
O

CH2

CH
o
CD2 t

CH2
O

CH
CD2

CD2CH=CH2
H

OH
CD2CH=CH2

2,4-

2,4-

.
2,6-,
-,
-.

1761

1762

.
CH3

OCH2CH=CD2
CH3 t o

CH3

CH3
CD2CH=CH2

2,4-
CH3

CH3

OH

CH3

CH3

CH2CH=CD2

H CH2CH=CD2
2,5-

,
.
. , ,
-

20 , (IV)
-78 .

.
. ,

,-

.
CH
250oC

CH2 CH O CH2 CH CH2

CH2

CH2

CH2

CH

CH2=CHCH2CH2CHO
50%

CH2

CH CH2
CH O CH
CH CH2

o
250 C

O
CH2 CH CH

CH CH2CH2

[3,3]-

26.

1762

1763

3.7.

, , .
,
- .
- MnO2
-.
OH

O
Na2Cr2O7
H2SO4 - H2O
-

,
, HCrO3-

, .
O

CrO3H
-HCrO3

O
HOH

+ H
H

OH

OH

O
Na2Cr2O7
H2SO4 - H2O
O

OH

-
, 1845 .

- ,
.
OH

(KO3S)2NO ,20 C
97%

H2O
O

1763

1764

-.
CH3O

NH2

(KO3S)2NO ,20 C CH3O

CH3

CH3

H2O -
O

96%

:
0-5 oC
H2O

NaNO2 + Na2S2O5 + CH3COOH

3(NaO3S)2N-OH + KMnO4

0-20 oC
H2O

2(NaO3S)2NO + 4KCl

(NaO3S)2N-OH + CH3COONa

3(NaO3S)2NO + MnO2 + KOH + H2O

0-5 oC
H2O

2(KO3S)2NO + 4NaCl

- -
.
:
, , , ,
.
O

OH

Na2Cr2O7,30 C
H2SO4,H2O

86-92%

OH

-.
NH2

O
Cl

Cl

Na2Cr2O7,10 C
H2SO4,H2O
O

OH

83%

,

.
OH
OH

Ag2O,0 C

1764

O
O

1765

, - 2,3,5,6-1,4- () 2,3,5,6--1,4-
-
, :
OH
CH3
OH

CH3

Cl

Cl
Cl

Cl

80 C

CH3

C6H6

CH3

Cl

OH

Cl

+
Cl

Cl
OH

1,4- 1,2-
, - .

.
, -
- , ,

. . (1953 ) . ,

2,4,6---

(III)

K3Fe(CN)6 -
- --,
.
(CH3)3C

OH

O
C(CH3)3

C(CH3)3

K3Fe(CN)6,NaOH

(CH3)3C

C6H6 - H2O

C(CH3)3

C(CH3)3

0,1
, .
, (IY), (II)
.
()
(III) -,
PbO2, ,
, .

1765

1766

(CH3)3C
HO

C(CH3)3

PbO2,20 C

O
C(CH3)3

C(CH3)3

(CH3)3C

C(CH3)3

N
C(CH3)3

O
C(CH3)3

70-80%

, - -
,
. ,
- ,
. , , 2,4,6-
(III) 95% ,
0,01 20 10%.
- 2,6---4- 3%- 70-75%.

- -, --
-- , -

-
. , ,
,
. : :
H

2
O

R
R

HO

R
H

R
O

OH

R
..

,
- , .

-, .

1766

1767

2,6----4-;

2,4,6-

2,6---

-4- ..
.
OH
C6H5

C6H5

C6H5

K3Fe(CN)6,KOH,

C6H5
O

C6H6-H2O

C6H5

C6H5

C6H5

C6H5

C6H5

.
, -
- . ,
2,4- 2,6-
.
OH
(CH3)3C

O
C(CH3)3 PbO
2

(CH3)3C

C(CH3)3

C(CH3)3
O

C(CH3)3
H

C(CH3)3

H
C(CH3)3

(CH3)3C

C(CH3)3

HO

OH
C(CH3)3 C(CH3)3

C(CH3)3
O

C(CH3)3

PbO2,

C(CH3)3

C(CH3)3

, - .

2,6-
: PbO2, Ag2O, K3Fe(CN)6.

, - -
- . , -

1767

1768

, .
, , ,
(III) ,
.
C(CH3)3

C(CH3)3
CH3

OH

PbO2; ;
CH3

O
C(CH3)3

C(CH3)3
C(CH3)3
CH3

OH

C(CH3)3

+ CH2

C(CH3)3

C(CH3)3

1,2-(3,5---4-) .
C(CH3)3

C(CH3)3
CH2

O
C(CH3)3

+ CH2

C(CH3)3
C(CH3)3

C(CH3)3
CH2 CH2

OH

OH
C(CH3)3

C(CH3)3

C(CH3)3

C(CH3)3

CH

CH

C(CH3)3

C(CH3)3

PbO2 .
,
- - - (2,6----4; 2,6----4- ..).

1768

1769

, ,
, .
PbO2 .
C(CH3)3

C(CH3)3

PbO2; ;
; 20 oC; 8

OH

CH2

OH

C(CH3)3

C(CH3)3

C(CH3)3

C(CH3)3
CH

O
C(CH3)3

O
C(CH3)3

-
. ,
.
,

.

4.
,
: ,
, ..
.
O

O
CH3

O
O
O
1,2-
(-)

1,4-
(-)

2--1,4-
()

O
O

CH3

OH

CH3

OCH3

3--2--5-1,4-
( )

O
O
2--1,4-

2,6-

1769

O
9,10-

1770

, , , ..
O

OH

OH

OH
CH3
OH

( )
1,2--9,10

(5-1,4-)

()
2--3-1,4-

O
OH
O
CH2
O

2-1,4-
(
)

CC

CH3
(CH2)3 CH (CH2)3 CH(CH2)3CH(CH3)2

CH3

CH3

1 ()
OH

OH

HO

O
CH3O

(CH2CH=C(CH3)CH2)10-H

CH3O

CH3

HO

CH2CH3
OH

( )

( Q10)

9,10-
, .
,
.
.
O

NH
NH

NH2

OC6H5

O
NH2

()

1770

1771

2- , :
O

NH2

NH

O
KOH,KClO3

NH

220-250 C
O

55%

4.1.

- ,
.

.
, 90%.
O

OH

(KO3S)2NO

(KO3S)2NO
-

ON(SO3K)2

97%

,
.
.
, ,
1,2- -.
OH
OH

Ag2CO3

100%

-
(65SeO)2O.
.
OH
R

(C6H5SeO)2O

O
O
50-60%

1771

1772

, 1,4 1,4-
(VI). (VI)
( ), ,
, , .
O

NH2
CH3

CH3

Na2Cr2O7,5 C
H2SO4 - H2O

44%
O
O

OH
o

Na2Cr2O7,30 C
H2SO4 - H2O

OH

1,4-, 9,10- 9,10-

(VI)
.
CH3

O
CH3

CrO3,CH3COOH

38-42%

O
O

CrO3,CH3COOH
44-48%

Na2Cr2O7,80-100 C
H2SO4 - H2O
O

86%

(V) .
.
O
o

+ O2

V2O5,320-390 C
70-80%
O

1772

1773

9,10-

.
O

O
C

AlCl3,C6H6,70 C

COOH

C
O
O
C

93%

H2SO4,100 C

COOH

85-90%

4.2.

. .

-, .
-.
-
.
O

+e
O

+e
O

, ..
, -,

1773

1774

OH

+ 2e + 2H
OH

O
o

E=E

2,303 RT

nF
o

25

E=E

+ 2
H

lg

, F-

- 0,059p + 0,296 lg

,
-,
, . ,

. 23-2 -
25.
23-2

- 25

1,2-

783

2,3--1,4-

499

1,4-

700

9,10-

130

2--1,4-

645

1,4-

400

2--1,4-

713

9,10-

440

1,2-

566

1,4-

520

1,4-

470

1,6-

610

2,6-

758

3,4,5,6--1,4-

740

2--1,4-

422

954

, 23-2, , 1,2-
, 1,4-,
,
.
. ,
- .
- ,

1774

1775

- 1:1
.
.
O
O

OH

OH

O
OH

+
O

OH

OH

OH

,
, - . ,
,
. -
, ; 1,3,5,

n- (, ) - ( ),
.

.
(
2). . , ,
1,3,5- (1,2,4,5) ,

, 0,1
.

1775

1776

,
Na2S2O4 .
O

O
CH3

CH3 Na S O ,NaOH
2 2 4
-
O

OH
CH3

HCl

OH

, (II) ,
. 1,4 (IV)
70-80.
O
o

OH

SO2,H2O,Fe,70-80 C
H2O
O

OH

9,10- 9,10 ().

O

OH
1)Na2S2O4,NaOH
2)HCl,H2O

OH

9,10-
- .
O

OH

Sn,HCl
CH3COOH
O

H H

,
. , ,
,
.

1776

1777

.
.
.
.
.
H
N

H
N

OH
+ 2e, +2H
O2

N
O
H

N
OH
H

4.2.2.

.
- ,
2,3,5,6--1,4- (); 2,3--5,6-1,4- (), . 1,2-

, ,
, ..
O

Cl

Cl

Cl

O
H

OH

Cl

C6H6,80 C

Cl
OH

H
Cl

Cl

Cl
O

Cl

Cl

Cl

OH
HBF4,C6H6

Cl

+
BF4

1777

Cl

Cl

Cl
OH

Cl

1778

O
Cl

CN

Cl

CN

80 oC
C6H6

CH2 CH2

O
OH
CH

Cl

CN

Cl

CN

CH

OH

,
,
.
-
, .
, .

4.2.3. ,-

1,4- ,-
1,2- 1,4-
(. 16). 1,4- 1,4 2-.
O

OH
Cl

HCl
O

OH

2- 2--1,4-,
HCl 2,3-.
OH

Cl

O
Cl

+
OH

1778

OH

+
OH

1779

O
Cl

OH
Cl

+ HCl

OH

Cl

2,3--5,6--1,4-
().
O

OH

+ 2 HCN

OH

OH

OH

CN

HNO3

HCl

CN

CN
O

HCl,H2O

CN

CN

OH
Cl
Cl

CN

HNO3

OH
CN

CN

CN

Cl

O
CN

Cl

OH

CN

CN

OH

OH

HNO3

Cl

OH

CN

Cl
O

CN
90%

1,4. 1,4 ,
- 2--6.
S CH(NH2)2

S
O

O + NH2

HCl

C NH2

HO

OH

OH
O

N
NH2 +

HO

+ H2O

S
OH

1,4- 1,2-
- .
1,4-.
1,4- 2,5-()1,4-.

1779

1780

NHC6H5
O

2C6H5NH2

HO

NHC6H5
O

OH

C6H5NH

+ HO

OH

C6H5NH

1,4- 1,4-
, .

4.2.4.

1,2 1,4-, 1,4-

-.
1,3- 1,4- 25 ,
.
, , .
(VI) 1,4-.
O
o

C6H6,20 C,48

O H
HCl,CH3COOH
O H

O
OH

O
CrO3,CH3COOH

OH

88%

76%

1,4-
1,3-.
1,4-

. - 1:1.
.

1780

1781

O H

O
CH3CH2OH

CH2

20 C,1,

O H

- 1:1-
O H

H O H
CH2

CH3CH2OH

CH2

90 C,5,

O H

CH2

H O H
--- 1:2-

,
1,3-.
1,2,3,5--1,4-

. 1,4-
.
1,2-
1,4-.
O
+

+
O
O
o

H2,Rh/C,20 C
O
o

Pd/C,300 C

,

.
.
1781

1782

,
,

.
Q,
. Q.
,
.
Q10 (. ).

.

1782

1783

24.

24.1. ....... 1785

24.2. ..................... 1789
24.2.1. ................................................................................................................... 1789
24.2.2. ...................................................................................................................... 1790
24.2.3. ................................................................................................................... 1791
24.2.4. 612.......................................................................................................... 1792
24.2.5. ..................................................................................... 1795
24.2.6. .................................................... 1797
24.2.7. ......................................................... 1799

24.3.
............................................................................................................................ 1801
24.4. -................................................................................... 1806
24.5. - 1808
24.6. . 1812
24.6.1. ...................................................................................... 1815

24.7. .... 1818

24.8. .......... 1821

24.9.
........................................................................................................................... 1824
24.10. 1825
24.11. ........................................................................ 1830
24.12. ,
......................................................................................................................... 1834

,
. ,
,
, ...
.
1883 , .-
. 1,2-
1,3-
-
. . " "
. .
1,3-.

1783

1784

.
, 1885 - .
,
.
,
. .
. ,
,
.
. ,

109 28' . ,
""
, .. 5444'. 1/2 (10929'-60) = +2444',
1/2 (10928'-90) = +9,44, +0,44, - -516' ..
-
- ,
,
. " "
.
,
. ,
,
. (1926-1930 )
- .
,
. ,
.
""

CH2
CH3

CH
C O
(CH2)12

CH2
CH2

C O
(CH2)12

(CH2)7
C O
HC
(CH2)7
HC

HC (CH2)5 C O
HC
(CH2)8 O

- ,

1784

1785
.
.

24.1.

,
, ,
( 4). Hof
25
. , ,
. 2; 2 .
-30,160,16 / 32,400,13 /.
4 + 5 2 -410; Hof = -30,160,16 /
4 + 5 2 -410; Hof = -32,400,13 /
- ,
, . ,
- 2,3 / , , -
-, .

CH3
CH3CHCH3 + H0;

CH3CH2CH2CH3

H0 = -2,3 /

-
. Hof ,
. .24.1
, , .
24.1
o

H f , ,

Hof,

/
H4

-17,9

Hof,

/
2,2--

Hof,

-44,5

+8,2

CH3CH3

-20,2

CH2=CH2

+12,6

-1,1

323

-24,9

3=2

+4,9

-2,2

1785

1786
3223

-30,1

-C5H12

-35,0

32=2

-0,2

HCCH

+54,3

-C6H14

-39,9

--2

-1,9

CH3CCH

+44,4

-C7H16

-44,8

--2

-3,0

CH3CH2CCH

+39,5

-C8H18

-49,9

--2

-7,0

CH3CCCH3

+34,7

-410

-32,4

--2

-7,9

CH2=C=CH2

+45,6

(3)223

-36,9

+37,5

CH2=CH-CH=CH2 +26,1

(3)4

-40,1

3-

-41,1

-6,5

+31,9

, .24.1, -

4,9 /, .. H0f 2-
4,9 /.
nH2n (2)n,
H0f 2- , H0f
n, .
-H0f/n -4,9 / .
24.2 H0f, -H0f/n .
, -H0f/n
-4,9 / , , .

,
, .

, ,
.
- . ,
, .

H0f/n -4,92

/. , ,
-4,92 8 = -59,4 /.
H0f/n -29,4 /.
-29,4-(-39,4)= +10 /.

1786

1787

.
(.24.3).
.
.24.1
36 - 1632.
:
24.2

H0f

H0f/n

+ 12,7

+ 4,2

27

+ 6,8

+ 1.7

26

- 18,4

- 3,7

- 29,5

- 4,92

714

- 28,2

- 4,0

816

- 29,4

- 3,7

10

918

- 31,7

- 3,5

12,5

1020

- 36,9

- 3,7

13

1122

- 42,9

- 3,9

11

1224

- 55,0

- 4,6

1530

- 72

- 4,8

1632

- 76,9

- 4,8

36 48, 510 , 612 714, " " 816 1122 .

:
, , -

)
10928'. - (
)

- ;
1 /.

. ,
, 8-11.

1787

1788

24.3

2-

499,8

166,6

27,6

655,9

164,0

26,4

793,5

158,7

6,5

944,5

157,4

1108

158,3

6,3

1269

158,6

9,6

1429

158,8

12,6

10

1586

158,6

12,0

11

1742

158,4

11,0

12

1891

157,6

2,4

13

2051

157,8

5,2

14

2204

157,4

157,4

E
3

30

4
25
20
15

9
8

10

10

13
11

12

6
2

10

12

14
14

16

.24.1.

1788

1789

24.2.
24.2.1.
--
60 -- 114. -- 49,5
-- , , .

114

o
1,510 A

60

o
1,089 A

2,

sp2-

-, .2.
, .

2, .
- ,
,
. , , ,
. 60
sx-
- .
. ,
- , - (83%) s-
(17%), -.
"" , "" -.
"" ,
, . ""
,
. 21. -
, , 1,510, ..
- (1,543) ,
s3- . C-C-

s5.

1789

1790

,
- , , s-
- s3- .
"" sp2 - sp2-
s- .
- , - . , (36-37)
, .
2-

-- 114.
, ,
, .
, . -
.
1 / ( 4).
6 / 27
/.

24.2.2.
,
,
90.
8 - , 8 /
.
, 25o
, :

107

88o

o
1,551 A

1790

25o

o
1,109 A

1791
,
, :

HH
H
H

:

H
H

H
H

H
R

H
H

H
H

H
H

H2C

CH2

H2C

- .

24.2.3.
108,
109,5. 510
- , 10 / .
" ":

H
H

o
1,546 A

104,5

H
H

H
H

o
1,113 A

106

H
o

- ,
.
510 6-6,5 /.
5,2 /.
,
,

1791

1792
"". ,
:

360 .
. , ..
.

24.2.4. 612
.
- ,
, . ,
, (.,
., 1950 ). ,
- .

He

H
a
5

H
a
3e
H e
o
H
1,536 A
o 4 a
107,5 H

eH
a 6
H

H
a 1
111

o
1,121 A

eH

eH
a 2
H

1-2
3

CH2

H
1

CH2

CH2

H
11

CH2

H
H

. ,
, ,
, 107,5 , . , ,
. -
,

1792

1793
,
- - . .

H
a
He
H e
4

H
a 1
eH
eH

a
aH H
3

He

a
H

a e
H

H
a

He

He

He

H
a

a
H

aH

a
H

eH

eH

e H

a
H

10,8 /. ,
: (-), -
. , .
- , 1
2,
3, 5, 6, 4. 1, 2
6. , ,
. ,
, - ,
7 / .
2
3, 5 6. , "" 1 4
1,83,
2,4. ""
3 /.

H
H

HH

CH2
CH2

H
H

H
H

C1

H
H
H

H
C6
H
C2
H

C5

H
H
C3
H

H
H

H
H

H
H

1793

C4

1794
1 4
. 1-4 , 2,
3, 5 5 , -.
.
C1
(1)

C6

(2)
(1)

C1

C6

(2)

(2)

C2

C3

C2

C3

- (1)

C4

C5

C5

C4

(1)

C2

C1

C4

C3

C6

C5

- (2)

-
"" 1 4, -
, . - -
, - , .
-
(-), .

,
,
. . 24.2.
,
.
,
- (1). - ""
- (2). -
(2),
- (2).

1794

1795

()
(1)

()
(2)
5,3

1,5

10,8

(2)

(1)
5,5

(2)

(1)

.24.2.
, - -.
(1) (2).

, :

-
( ).
20 99,99% ,
25.

24.2.5.

. , ,
,
, -
, -.
-- .

1795

1796

,
5-7 /.
,
. ,
, ,
- .

H
H

H
H
,
.
,
.
,

--.

. , .
-- , - .
.

H
H

H
H

(--)

H

- . ,
.

1796

1797

24.2.6.
,

, ,
.

H
H C
H
a
e C
H
(5%)

H
H

(95%)

= / = 20; G0 = -1,8 /

, (.. 8).
- - , ,

, -120
.
, .
25 95% - 5% -. -
- ,

(1)-(2) .
.
3

CH2

CH3
1

CH2

60

CH2
3

CH2

CH3

H
H

-
2- (3),
()-.
(3)
(-) ( 4). , -
0,9 /.
- , (3) (5),
0,92, .. 1,8 /.
- -
.
--
3- (3) (5).

1797

1798
1,3- 1,3- .
- .

H
H

H
C

- - 611
G
X. 611
- ,

13

.
.
105 -1 .
101-102 -1
.
, . 6D10l +25
, -60oC , -150oC
, (.24.3).
.
a+b
2

D
H
D D
D

D
D

D
Cl
D

DD D

Cl

+25 C

-60 C
o

-150 C

.24.3. +25; -60 -150

-150 .

.24.4

13

-100. G,
-.
G

3 ~ CH3CH2 < CH(CH3)2 < C(CH3)3. -

G, 5,4 /. 25 1-2 10000 .. 0,01% .
24.4

1798

1799

G, /

G, /

-0,25

C6H5

-3,1

Cl

-0,58

CN

-0,2

Br

-0,48

COOH

-1,85

-0,45

OCOCH3

-0,7

CH3

-1,8

OH

-0,87

CH2CH3

-1,8

OCH3

-0,55

CH(CH3)2

-2,1

OTs

-0,52

C(CH3)3

-5,4

CCH

-0,41

NO2

-1,16

-
. , , ,
. 25
,
.

24.2.7.
1,2; 1,3 1,4- , - .
.
.
- 1,4- ,-
,-.

CH3
a
H

CH3
a
G0=0

CH3 e
a,e-

H e,a-

e CH
3
H

-1,4-

G0 = 0
-1,4- , G0 = 0. 1,4- (,),
(,) G0 = -3,4 /.

1799

1800

CH3
a
H
H

G0=-3,4 /CH3

a a,a-
CH3

e,e-

e CH
3
H

-1,4-

G0 = -3,4 /

- - 1,2-
, - - 1,4- .
-1,3- ,
:

CH3
a

CH3
a
H

CH3 e
e CH
3

e,e-

a,a-

-1,3-

-1,3- , .

CH3
a

H
H

e CH3

a
CH3

e,a-

a,e-

CH3

-1,3-

, - - 1,3-

- - 1,4- 1,2- . , 1,2- 1,4-

- 1,9 / , -. 1,3

.
,
.

-1,3---

. -
. -1,3---

1800

1801
, ,- ,-
:

H C H
a H
H
H Ca
H
H

e C(CH3)3

e,a-

a,e-

e C(CH )
3 3
H

-1,3---
, - .

H
(CH3)3C

e
e C(CH3)3
H

- -
-3 -5, -
.

24.3.


.
,
.

- . ,
, -4--1--
, - .
- -4--1--
.

1801

1802

Br

e
Br

H
(CH3)3C

(CH3)3C

e
H

-4--1--

-4--1--

SN2 , ,
Y- , ,
.. - -, - -.

82

Br*

e
H

H
e

(CH3)3C

(CH3)3C

(CH3)3C

H
e

Br

a
e
Br

Br*

e
(CH3)3C
H

Br*
H

82

Br*
+ Br

+ Br

.
,
- -, ..
. -
,
, - .
- SN2-
. , -

82

r-

, -. .
- -4--
. SN1- ,
, -
- s-,
.
-4--
4 2,3 , -,

1802

1803

(.24.4).

G = Ge - Ga
Ge

Ga
- OTs-

G - OTs-
.24.4. - - 4-

.
3-6 , -. 24.5

.
24.5

90%-
3
K, /.

(I)

13,2

OH

(II)

51,3

(III)

42,0

(IV)

123

(V)

146

OH

(CH3)3C

(CH3)3C

(CH3)3C

OH
CH
3
e

OH
a

(CH3)3C

CH3

OH
a

(CH3)3C

CH3

1803

1804
, .24.5, , ,
. ,
- .
, . ,
II I c , -,
, .
II IV, ,
. ,
IV V .

sp3-
sp2- .
, ,
24.4, , ,
.
2-
.
2-
- ( 10).
1,2-
X. , ,
. , ,
2- l . , ,
, . ,
.
,
, .

CH3
CH3 a

H
H
(CH3)2CH e

Cl
H

CH3

CH3

H
CH3CH2O

a
a

Cl

o
H ; 80 C

CH3

CH(CH3)2
-2

-2
. , ,
-3 .

1804

1805
, ..
.

.
.
- -3 (75%) -2 (25%). -3 ,
, ,
- .

CH3

H
Cl

CH3 CH3CH2O

(CH3)2CH

CH3

CH(CH3)2

CH(CH3)2

-3 (75%)

-2 (25%

1,1,2 -. 1,1,2-

-,

82

Br 1-. -82,

, 1-
-,
- 1-, 82r.

Br
Br*
H
Br*

Br
+ Br2*

Br

Br*
H
Br

+ I

+ IBr2*

Br*

- -
. -82,
, ,
-.

SN2-

, ,
, .
, ,
. - 4- OOR 20

1805

1806
-,
.

COOC2H5

COONa
+ NaOH

(CH3)3C

(CH3)3C

COONa

COOC2H5
+ NaOH

(CH3)3C

(CH3)3C
-

CH3CH2O-C(OH)-- -.
,-
- -.
-4---

-.

24.4. -
-
. G0
1 ,
, ( ),
. , ,
/ /1
, , , 1.

A1

G0 ,
,
. ,
- (1954 )
(.24.6).

1806

1807

(2)

GC GB

(1)

Ga

GC

GB
A1
G0

.24.6.
/ G0, G - GB > GA,
.
- 1--1,2-
-
-.
CH CH ONa

C6H5CH2CHC6H5 CH3CH2OH
3
2
Cl

C6H5
H

H
C6H5

C6H5

C6H5

, , - -
, - 1. ,
, ,

Cl
H
C6H5

Cl
H

C6H5

H
H

C6H5

C6H5
H
1

G - GB, G0.
: ,
(2) G+G0.
G. , 1,
G0, , . ,

1807

1808
1 (2),
1. .
(1) 1.
(1) (2)
G- GB- G0, G GB >> G0.
-
, .

.
. ,

- .
G0

CH3COCH2COOCH2CH3

CH3C=CHCOOCH2CH3
OH

,
, G ,
G0^ .

.
92% - 8% . (, , ) , .

24.5. -

-

.
,
, -
"". ,
,
G0 . ,

, . , , ,
24.3.
G0( 24.4)
.

1808

1809
.
"" ,
. -.
,
. -
, -
:

10

H
2

10

a
7

2
4

H
(2; 3)*

(2; 3)*

18

- ,
-

- -.
,
- , , ,

19
1
2a

3e
4a

11a

CH3

C
9 H

10 H
5 B

18

CH3

12 e

6a

8
7e

13 D
14

C8H17

18

17e
16

19

CH3()

15a

A
3

10

H()

CH3()

11 12

B
5

H()

H()

13

17

C8H17

14 15

H() 16

5-

5- -
,
- 5-c. ,
- ,
- (.. -). 10 13-
, .
, , -

18

-,

, -, . -c
, - - .

1809

1810
,
.
, ,
,
, . ,
5--2 20 ,
5--2 <^.
,
, .
- E2--
,
. , , 11, 12--5 , ,
- 11-, 12-,
. -

, - .
35--2 ,

36 , 2--5---3
75 .

OH
a
OH
30

OH

75

Br

HO e

Br
-, ,

,
.

. , -3
3,-4-

Br
Br2
CHCl3

Br

.
, .

1810

1811
,
.
: (),
() ().
. ,
, , , .
.
.
.
( ) .
CH3
CH3
CH3

OH
H

CH3

H
H

OH
H

CH3
CH3

H
H

H
HO

H
H

. () - ,
.
CH3
H

OH

CH3

H
O

CH3

CH

H
H

OH
C

OH
C

H
H

H3CO

.
, .
200 300 .
.
, ,
. ,
, .

1811

1812

CH3
CH3
CH3

CH3
CHHCH2CH2CH2CHCH3
CH3

H
H

HO

HO

CHCH2CH2COOH

CH3

H
H

CH3

OH

OH
H

24.6. .

-
,
.
,
.
,
,
,
.
.

O
O

HN

1,3-

1,4-

1,3-

S
O

1,4-

- .

-5---2--1,8-,

- . -
1,3- ,

1812

1813
. , , .

C(CH3)3

O
CH3 e

, 1,3-
-2. ,
, 2- l4
83%, 2- 95%.

O
e

OCH3

CCl4
20 o C

OCH3

H 83%

H 17%

OCH2CCl3

O
e

OCH2CCl3

CCl4
20 o C

5%

95%

2-,

70 95%, 2-, 2 ,
N3; NHAc; ... 1,3- 1,3- -
-2 ,
, . -2,3--1,4-, 1,4 .

Cl

Cl
a

O
a

H
S

S
a

H
H

Cl

Cl

, .

, .
,
, . ----D .

1813

1814

OAc

Cl
a

a
a

AcO
AcO

OAc

OAc

OAc

Cl

24.6

B
X

Y
A

CCl4

CS2

B
Y

A
A

Y
B

2--

O-C-Cl

CH2

Cl

98-100

O-C-CH3

CH2

OCH3

83

2-

S-C-Cl

CH2

Cl

93

2--1,4-

O-C-Cl

Cl

100

2-

S-C-Cl

Cl

100

2-

S-C-OCH3

CH2

OCH3

90

2--1,4-

O-C-OCH3

OCH3

80

O-C-SCH3

CH2

SCH3

90

S-C-SCH3

CH2

SCH3

60

-
2-

2-
2-

-
.

. ,
.

1814

1815

24.6.1.
,
. 32-.

n ( s3- , ):

H
H C
H

C H

n-
-.

*CH

*CH

X, .
, 22- CX* CH* , . , CX* ( CH*) n,
.

*CH

*CX

CX* , CH*,
. .
, -
- (ns-CX*) (ns- CH*).
. I
3-
. H2, -
(, NH2), 2,
II III:

1815

1816

(I)

H C O
H
H

H
X

(II)

H C O
H
H

H
X

H
H C O
H

(III)

- II
s* -. - III
CH*, - CX*. CX*
nO, CH*, (nO-CX*) ,
(nO-CH*). , - III .
CH3CH2- 3 ,
,
. ,
3 n n :

n
n

H
CH2X

n , n. ,
,
CX* CH* (n-CX*), .

CH*

CX*

n
n

, () --- 90

H
H

1816

1817
: (n-CH*), (n-CX*), (n-CH*),
- ( --- 30o)
, 90o.
, ,
: - 2 ,
CX*.
,
2-- 2--
- 2.

O
X

X H

X
H

,
. (n-CX*)
, , -O .

Ox
CX*

CX*, X, .. .

-O -l -2,3--1,4-:

O Cl

Cl

C2-O1

1,394

C3-O4

1,428

C2-Cl

1,819

C3-Cl

1,781

2-l O1. 3-l

4. 2-O1 3O4, 2-l 3-l.

-,
- CX*. , 2,4,6-1,3- IV V IV

1817

1818
, 2-, V
. , 2- IV , V.
, , 2, - IV , V.

CH3
O

O
IV

CH3
O

IV
+t-BuO

+t-BuO

-t-BuOH

-t-BuOH

CH3
O

24.7.

70% .
1887 1,3- .
.
NaI; Na2CO3
CH3CH2OH; 80 oC

BrCH2CH2CH2Br + Zn

+ ZnBr2
70%

1,2-

( 17).
( 5).
.
, . 1885 . ,-
.

25)

1,3-

H
HC COOCH2CH3
HC COOCH2CH3

+ CH2

N N

1818

CH2

C COOCH2CH3

N N C COOCH2CH3
H

1819

H
HC COOCH2CH3
CH3CH2OOC

+ CH2

HC

C COOCH2CH3

CH2

N N

N N

H
COOCH2CH3

C2H5OOC

H
C COOCH2CH3

CH2
N N

C2H5OOC

C COOCH2CH3
H

COOC2H5

COOC2H5

CH3
CH2

CH3
H

CH3 t oC

CH3

CH3

CH3

-(1,3)-.
, -
, N (O)R .

ClCH2CH2CH2CN

CN

NaNH2

1,3-,

67%

42-44%

-1,1- .
,

.
[2+2]
.
- ( 25) , ,
,
.

. - - .
[2+2]

1819

1820

([2.2.1]-2,5-) - .
= 205

75%

95%,
313 .
.

O
h

2
O

[2+2]
, , a.

Br
h

Br

COOH

OH

Br

Br

HOOC

,- ,

.

CN

CN
+ CH2=CH2

-
.

O
C6H5C

C6H5
H

1820

70%

1821

O
(C6H5)2C=O + (CH3)2C=CH2

h 10 o C
C6H6

C6H5
C6H5

CH3
CH3 93%

3,3--2,2-
ZnCl2 10 oC

H2C=O + CH2=C=O

-2-
(-)

88%

, ,
1,4- 1,5-.
, ,
CF3SO3Ag.
- -.
.

Cl

H
1) Mg;
2) CF3SO3Ag

Cl
Cl
Cl

61%

1) Mg;
2) CF3SO3Ag

82%

24.8.

: ,
,
, .
,
.
CH3CH2CH3

H2; Ni; 120 oC

CH3CH2OH

H2; Ni; 120 o C

CH3CH2OH

1821

CH3CH2CH3

1822

CH3

H2; Pt; 80 oC
CH3CH2OH

91%

CH3

[4,2]

.
.

CH3
CH3

Br
HBr
H2O-CH3CCH2OH

CH3

C CH2CH3
CH3

,
300.
. ,
.., .
.

CH3
CH3
NaBr

CH3
+ Hg(OAc)2

-
t oC

CH3

OH

CH3
CH3

C CH2CH2HgOAc

C CH2CH2HgBr
OH

,
, , 1,3.
Cl2

Cl2
h

Cl(CH2)3Cl h >100 oC
Br2
h

Cl + HCl

Br(CH2)3Br + HBr

- .
,
- .

O
1) O3; CH2Cl2; -78 o C
2) H2O2; CH3COOH

+
O

1822

1823

-1,2-

-1,2- :

C6H5

1) O3; CH2Cl2; -78oC

2) H2O2; CH3COOH

C6H5

COOH
HOOC

- ,
s- -
- . 36-38
- - .
-
.

+ C4H9Li
C6H5

-30 oC

(CH3)3CO K
25 oC

C4H10 +

Li

C6H5 + (CH3)3COH
K

,

.
, .
, ,
. 150
-. 300.
, -
, ,
4. -
.
,
-, -
1,3-.
-
1,4-, 1,5- 1,6- .
, 1,5-
, 1,6- - .
( 12). ,
,
.

1823

1824

24.9.

,- , 17.

(CH2)n

COOCH2CH3
COOCH2CH3

(CH3)3SiCl

(CH2)n

Na
; 140 o C

C-OSi(CH3)3

H3O
H2O

C-OSi(CH3)3

(CH2)n

C-ONa
C-ONa

(CH2)n

C=O
C-OH

50-95%

n = 6-27

,-

. .
,

. , , , .. 10-5 .

, ,-
.
. .
(1933 .)
,
65-NLi-23.
,
-() .

1824

1825

(CH2)n

CH2C N

LiN

CH2C N

(CH2)n

CH2CH3

(CH2)n

C6H5

CH-C N
Li

CH2C N
CH-C N

Li

CH2C N

H3O
H2O
t oC

CH2

(CH2)n CH COOH

-CO2

CH2

(CH2)n CH2

.
95
88%, , ,
60 80%.
() 60%.
9-13 1-8% -
.
-, -
( 16) 5% n>15
9-12.
7
1,3- 1,3-

-.

-, -
.

.

24.10.

,

1825

1826

(3-4),
(5-7), (8-11) . ,

6 / 12-13
/ 9-11 .

- ,

-
.

. , , 8-11
, ..
. .

,
,
, .
1950-1960 , .
.
.
- ,
-1,2-,
(., 1952 .).

--1,2,

-1,4. 1,4- ,
,
- ,
.

-.
-

1826

1827

1-3 1-5, --1,4.

- ,
-,

- -1,4.
OH
+

HC(O)OOH
HCOOH-H2O

OH

H2O

OH

-1,2-

OH

OH
1,5~H

5
4

H2O

- H+

OH HO

-3--1

H
H

OH
- H+

1,3~H

1
2

- H+

- H+

-3--1

H2O

OH

OH

OH

--1,4

OH

-4--1

HO

--1,4

-
: -3-1 -4--1.
,
-.

-1,4, .. -
.
9-, 10-, 11-
1,2- - ""
. -
--1,6 --1. (., 1952 .).

1827

1828

H OH

OH
HC(O)OOH
HCOOH-H2O

+
H

HO
--1,6

--1

,
. ,
, 1,5- -
-5,
.
O

OH
+

HC(O)OOH
HCOOH-H2O

OH
4
3

OH

1,5~H

H2O

H
2

OH

HO
--1,6

-
-1 -6
-6 --2.

OH
2
3
4
5

H
- H+

OH
--2

- --1,6.

, ,
-1,2-,
.
-
1828

1829

1--1,6
1--6.

CH3
+

HO

H
OH

O H
H

CH3

CH3
- H+

- H2O
O

1
.
- 6, 1.
6
1--6.
-
. , ,
-5--

,
1,5- - .

OTs

(CH3)3C e

CH3COOH

(CH3)3C

H
1,5~H

(CH3)3C

- H+
99%

(CH3)3C

- 1,5 1,6- ().

OH

O
HClO4

CH3

CH3

ClO4

,
(..,
..).

H
N
O

N
O
OH

1829

1830

. , , -,-1,5 .

.

Br
+ Br2
Br

24.11.
, .
-, -
, , -

. , , -, -. 8-10 -
, , - ""
,
, , - (. 24.7).
24.7
- -
H-H

H-H

-9,7

+0,1

-2,8

+0,4

-3,5

+1,2

Ni(OAc)2; NaBH4
CH3CH2OH; H2NCH2CH2NH2

- ,

1830

1831

-33 .

H
Na
.; -33 oC

, -
(. 5). - -

. -

(-)

-2-Ni

,

-.

-,

, .. - .
- (2:3), -.
(CH2)n-2

CH2

120-160 o C

CH N(CH3)3 OH

H2O

(CH2)n-2

CH
CH

+ N(CH3)3 + H2O

n = 5, 6, 7 -
n = 8, 9 - -
n = 10-12 -

N(CH3)3 OH

110-120 o C

H2O

89% (/ = 2:3)

, , .
55 / (280 /),
(27 /) .
.. 1928 ,
. -

1831

1832

Cl(CH2)3CN

NaNH2

CONH2
CH3I

CN

1) HCl; ;
2) CH3CH2OH

Br2; CH3ONa
CH3OH

N(CH3)3I

NH2Cl

t oC

OC2H5
1) H O

NHCOOCH3 2) H2O2+
3

AgOH

NH2

325 oC

N(CH3)3OH

+ N(CH3)3 + H2O

.
-196, -80 .

.
.. 1986-1940 .
1,2- ,

,

Br2
CHCl3

Cl
Cl

PCl5

Cl
Br
Br
H
+

Cl
KOH
C2H5OH; 80 o C

Cl
Zn Na

KOH
C2H5OH; 80 o C

Br
+

.
1,2--1
- .

1832

1833

(CH2)4

Br

Na

Br

(CH2)4
(CH2)4

Br

Na

Br

,
.
,

.

,
,

1,3-

1,2-
. . . 9 70%.

(CH2)n-2

-2N2

(CH2)n-2

N NH2
N NH2
(CH2)n-2

HgO; KOH;
C6H6; 80 o C

(CH2)n-2

Pb(OAc)2
o
CH
NH2
2Cl2; -70 C

n = 8 52%
n = 9 63%
n = 10 67%

N N:

n = 8 9%
n = 9 39%

+ 2N 2

N NH2
N

N N:

(CH2)n-2

+ Pb(OAc)2 + CH3COOH + N2

1833

1834
, 1,2-
9%, 89%.
52%, 68%, 67%,
1--1,2,3-
-78. 21 /,
14,5 /.
,
80 50 /, .
.,
""
- 2,3,4,5- ("").
.
98% 88%, .

(CH2)n-2
N

NH2

N NH2

(CH2)n-2

N NH2

C 6H5

C 6H 5

C 6H5

C 6H 5

(CH2)n-2

Pb(OAc)2
CH2Cl2; -78 oC
C5H5N

C6H5
C6H5

(CH2)n-2
n = 6-7

+ CO
C6H5
C6H5

82 / 1
-78 2 -25, -110.
20,
.

24.12. ,

-, - ,
, .
,
, ,
, .
- ,
.
, , .
[2,2] 63 /.
1896

1834

1835
.
. .
, ,
().

BrCH2

Zn;
-

CH2Br

BrCH2

CH2Br

+ 2ZnBr2

[2,2]

BrCH2

CH2Br

+ 4e-

; LiBr; 40 V
4 ; 20 oC

CH2Br

BrCH2

+ 4Br

,
.
,
:

[3]- [6]-.

[6]-

[3]-

,
, (.., 1990 .).

1,1- -.
-
-.
,
, .

Cl
CH3CHCl2; -C4H9Li [CH3CCl]
CH2 -; 0 oC

CH3

45%
(CH3)3COK

CH2 CH2N2; Pd(OAc)2

70%

1835

80%

1836

CH3CHCl2; -C4H9Li [CH3CCl]

-; 0 oC

CH2
(CH3)3COK

45%

Cl
CH3

CH2N2; Pd(OAc)2

H2
75%

85%

CH3

CH3CHCl2; -C4H9Li [CH3CCl]

H2 -; 0 oC

60%

Cl

(CH3)3COK

CH2N2; Pd(OAc)2

CH2

..
90%

80%

0f

,
.

66 /
[1.1.0]. 95%
1--3-
.

Br
H

Na-K

..
95%

Br
.

CH3

CH3

Br Li-Hg

CH3

CH3

Br
CH3

Br _ ;LiBr; 40V
+ 4e
o

CH3

20 ; 16

CH3
55-90%

CH3

Br

1836

1837

-3:

CH2=CH-CH2-CH=N=N

CH2

CH

CH
CH2

3-

Br

COOCH3

NaH

COOCH3

, .
,
.

4-

1,1,1

5-

1837

3-

1838

; .. 430

60

, -
, ,
.
,
.
,
.

[4.2.02,5.03,8.04,7]; [1.1.1]- ,

.
(., 1964 ) -, [2+2]- - ()
, .

1838

1839

Br

Br

Br

Br2

NBS
CCl4

KOH

Br
O

Br

Br

Br
O

O
O
Br

COOH

OH

Br

HOOC

-,

--

1,3-
.

COOH
HOOC

1) SOCl2
2) (CH3)3COOH

COOC(CH3)3

(CH3)3COOC

(CH3 )2 CH
CH(CH3)2

150 oC

, 157 /,
. [1.1.1]-
, " "
, , - -
! [1.1.1]: -
--, . , -
.

1839

1840

CH2
CH2

CH2
C

[1,1,1]

. [1.1.1-]
1,3-
[1.1.1|.

Br
Br2
h

1,3-[1.1.1]

Br
Br
1-[1.1.1]

HBr
h

Br
CBr4

1--3- [1.1.1]

CBr3
[1.1.1]-
1,1--2,2().
3--2--1.

Ph3P-CH2 +

ClCH2
ClCH2

ClCH2

C O

ClCH2

0 oC

ClCH2
ClCH2

C CH2
Br

Br

NaOH; PhCH N(CH CH ) Cl

CH2Cl

2
2
3 3
C CH2 + CHBr3 CHBr /H O; 12
oC
;
0-5
3 2

40-45%

1840

CH2Cl

1841

Br

Br
CH2Cl + CH3Li

50%

CH2Cl
[1.1.1] ( )
- --
1978 . -- --.

(CH3)3C

C(CH3)3

(CH3)3C

C(CH3)3

= 254

-263 oC

(CH3)3C

C(CH3)3

(CH3)3C

C(CH3)3
O

O
(CH3)3C

C(CH3)3
+ CO

(CH3)3C
(CH3)3C

(CH3)3C

C(CH3)3

C(CH3)3

C(CH3)3
135 oC

h = 254

-263 oC

(CH3)3C

C(CH3)3

(CH3)3C

C(CH3)3

--
180-137 /. -- ,
--,
113 /.

.
,
(. .8).
(aten (.) - ).
, :

1841

1842

[2]

[3]

. ,
, .
-.
c DCl.
,

C34H63D5.
. "" , ,
, [2]-. ,

.
, .

CH2-COOC2H5
(CH2)30

1) Na; c
+
2) H3O ; H2O

CH2
(CH2)30

CH2-COOC2H5
Zn/Hg; DCl

C4H3D

(CH2)30 C4H3D

(CH2)32
COOC2H5

(CH2)30

CH2

C=O
CH-OH

1) Na; c
2) H3O+; H2O

COOC2H5

C4H3D

(CH2)32
CHOH

(CH2)30

C
O

[3]-.

O
CH3

C
O

CH3OOC

(CH2)12

(CH2)12

OCOCH3
(CH2)12

1842

C O
(CH2)12

~1%

1843

COCH3

(CH2)12
(CH2)12
O C

AcO

OAc

AcO

(CH2)12

(CH2)12

(CH2)12

(CH2)12

O O

OAc C O

AcO

CN
NC
CH3 CH3

OAc

(CH2)12

N
COCH3

(CH2)12

, .,
1964 . [rota (.) , axis - ). 1968 .
[2]-c.

OH O
CH C
(CH2)10

(C6H5)3CO

OC(C6H5)3

(CH2)28
24.8

, /

C3H6

-127

-33

0,68 -33

C4H8

-90-50

12

0,72 0

C5H10

-93

49

0,75

C6H12

6,5

81

0,78

C7H14

-12

118

0,81

C8H16

14

150

0,83

C9H18

11

-178

0,85

C10H20

10

201

0,86

C11H22

-7

91 12

0,86

C12H24

61

160 100

0,86

C14H28

53

143 16 .

0,86

C15H30

60

110 1

0,86

C16H32

57

170 20

0,85

1843

1844

25.

25.1.
25.1.1.
25.1.2.

25.2.
2.2.1. -
25.2.1..
25.2.1..
25.2.1..
25.2.1..
25.2.2.
25.2.2..
25.2.2..

25.3.
25.3.1. -
25.3.1.a.
25.3.1..
25.3.1.. -
25.3.1.. -
25.3.1.. (4+2)-
25.3.1..
25.3.2. 1,3- ! .
25.3.2.. 1.3- ! .
25.3.2.. ! .
25.3.2.. 1,3-
! .
25.3.2. . 1,3-
! .
25.3.2.. ! .
26.3.3.
! .
25.3.3.. e ! .
25.3.3.. (2+2+2) ! .

25.4.
! .
25.4.1. (2+2) ! .
26.4.1.. (2+2)-
! .
25.4.1.. (2+2)-
! .
26.4.1.. (2+2)- ! .
25. 4.1.. (2+2)- ! .
25.4.2. (2+2)- ! .

25.5. ! .
25.5.1. ! .
25.5.2. ! .
25.5.2.. ! .
25.5.2..
! .
25.5.3. ! .
25.5.3.. ! .
25.5.3.. ! .

1844

1845
25.5.4.. ! .
25.5.4.. ! .
25.5.4.
! .

25.1.
25.1.1.
,
. ,
, .
1.

- ( . 7), ,
-1,3- , (), . .
( ) -
:
()

-1,3-

- , .
(
; . 25.3.1), -
. , ,
,
.

1845

1846
(, (. 2)
,
).

1,3 , ,
1,3-,
,
, 5- .
.. ..
CH2-N=N

CH2=N=N
..

1,3-

CH2

1,3-

,
. ,
; :
N

N
N

+CH2

( ).
.
, -

("") (, "", " ", .., "").
SO2, .

+ :SO2

SO2

SO2
2,3-5,5-

+ :CH2

H2C

1846

1847

Cl
+

Cl
P

:P
R

Cl
Cl
R
Cl

Cl
P Cl
R

Cl
R

2. . ,
,
-, ,

-.

-1,3,5-
-1,3- ,

1,3-,- ,
,
80 oC

AcOH

H
Cl

Cl

OAc

(.. 26).
3. .
- , [1,1] [i,j],
[i,j]- ( [i,j]- ).
.
[3,3]- , ..
[1,1] [3,3]:

1847

1848

1
1'

3'

2'

1
1'

3'

2'

3
3'

1'

2'

1,5-

1,5-

[3,3]- .
1' 1

2'

1'
O

3' 3

1'
O

1
2'

2
3' 3

1
2'

3'

1'

2
3

HO

2' 3'

2
3

H
-

[3,3]- (..
3 3 ), ""
, .. .

[1,2] - .
1

H3C

C
1'

C
2'

CH3
+
C C
1' 2'

C
1'

C
2'

CH3

, -
.
.
"" rikiklo, "".

(, , ).
, .
, .

25.1.2.
?
. -, ,

- .
.

1848

1849

16 !

NC
CN
Br

+ Cu

CN

CN

NC

(26.1)

-, ,
(.. 100%). :

CH3
CH3
Cl

CH3
Cl

-100 oC

CH3

CH3

SbF5/SO2ClF
-100 oC

H3C
Cl

+
H3C

H
H

H3C
Cl

+
H

-100 oC

CH3

H
Cl

+
H

Cl

H ~100%
CH3

CH3

H ~100%

H ~100%
CH3

-, -, ..
,
. :

COOH

COOH
COOH
+

COOH

90%

1849

" "

1850

COOH

COOH

" "

10%

COOH

COOH

-
, , ,
.
-,
, -. ,
, , ..
. ,
, ,
; h. ,
,
. , ,
, . .

Ph

Ph

[3,3]-

Ph
:

Ph

-9,10

1-[2.2.1]

(26.2)
-9,10

, ,
XIX , 1965 ., . .
-
. , ,

1850

1851
; ,
. ,
.

25.2.

- , . 26
. ,
,
-
. . 2 ( 2.4);
, ,
(I).
- (II), - (III) --. ,
,
- ( ,
-). ,
- (II) ,

. 2
-.

III

II

: 1)
, 2) 3)
"" . ,
.

2.2.1. -

25.2.1..

( 2.3.7,
. 2). .

1851

1852

. ,
,
. , ,
, , .
: ?

(. . 2, 2.2.4),
. :
()

()

()

- - .
-, -
( -, -
) . -
. -
- , (,
- - a)
.
.
. 2 ( 2.3.3) :
, - (2=2)2,
(2 2=2) ? (, " "
(2=2)2 , ,
, -. -
, .
" " , -
.
,
. -,
).
- - -.
, o 25.1. -
, - , ..

1852

1853
( 25.1
). / / ,
. ,
(/) (/) .
2 (. 1, 1.6), .. (2=2)2
,
.
25.1.

*- *'

*'

* + *'
- '

'

+ '

, , , ..
, ,
.
-
.

, ,
:
()*

+ ()

()

,
25.2.
25.2

1853

1854

*'

* + *'
- '

'

He2*,
-, , (. . 1, 1.6).
"" , ..
,
( ) . ,
.
:

CH2

CH2 + CH2

CH2 CH2 ( )

CH2

CH2 CH2 ( )

CH2 CH2
CH2 CH2

()

(
)

,
.
-. -
,
, :

()
()

1854

()

1855
: -
( - -
- ).
-,
(.2). . 2.8 (. 2) - , , .
( )
. .
,
( ) .
- ( 25.3). "" .
- ""
, .. - () , - ()
.
25.3.
()

*
4

(
)

()
*

*
3

-
. ,
, . 25.4 ,

e.
(2+) (3) , 2 3
(). ( 25.2)
: () (+) ,
* . , -.
.

1855

1856
C 25.4

3* -
A *

*
3

2
1

+ 2*

,
, , , ,
.
"" "" ? "
" " " ,
, . , "",
"" .
60-120 /, ..
.
.
, , ,
, , ..
.
, - ""
, "" ,
"'' ,
"" . ""
25.5.2..
. .
. , 2- :

H3

, ,
, , ,
, - . ? ,

1856

1857
, , , :
3
, , , -.
, -, , ..
.
. , 2- N (-), , , .
-M

N - - , ,
- .
(R, NO2, N2 .)
,
. .
, . ,

O
CH C
O
CH C

NC

CN

NC

CN

O
, (-)-.

25.2.1..

: 1) ,

, 2) ( ) 3)
.
, ,
(2+2), - (4+2) (4 + 2
). 1,3,5- (6+2),
1,5-- (IV) (4+4),
4- (V) - (4+2), ..
.

1857

1858

(6+2)

(4+4)
IV
(4+2)
V

, .. - -,
, ,
. , - (2+2)-,
- (4+2). -
(2+2), - (2+2+2).

(2+2)

(2+2+2)

, -, e, -
- .
-
, ,
. .

. .25.1 ,
; "+" ,
"-" .
2s

()

(2s+2s) , .. +

2s

1858

1859
2a
2a

(2a+2a) , ..

()

2s
2a

(2s+2a) , ..

()

.25.1. "" (24)2

"" ""

- -
, -; -
- , - - (.25.1) .
() - ,
; - -
, - -
(. 25.1 ).
- (
) . ( ) .
s .
. 25.1; o
- .
.
,
(2s+2s) ( "" .25.1), (2a+2a) (
"") (2s+2a) ( ""). : (2s+2s),
(2a+2a) (2s+2a).
25.1.

(s)

1859

1860

(a)

...

...

s-

...

(s)

...

(a)

(s)

(a)

, sp3, sp2 s-,

,
. -
, .
-
()
-

(s)

(a)

sp3, sp2 sp-

(s)

(a)

,
,
. () ()?
,

1860

1861
, .25.1 . ,
() () - ,
- . . ()
, ..
. , , (), () (), .
- , ()
? , " " "
"

""

()

, -, , ..
- . -
, -
-. , -
. , (),
, . , ()
- , o
() - .
-, , :
()

()

(4+2) -

(4s+2s) -

()

()

(4+2s) -

(4s+2) -

() () , () , -
.
= ,
-.

1861

1862

25.2.1..
-

, .
, ,
. ,
.
, , .
, .
,
, , - .
.

(2s+2s)-
.
,
, , , ,
, :

'

'

C2

C2

, (2=2)2
. ,
"" , -
( 25.2.1.), ""
. ""
.

, (2=2)2
(2)4. ,
(
20). , (2=2)2 (2)4 ()
() 2, .
2 , , ,

1862

1863
, .19
, (2=2)2 (2)4
, 2 .

.

.
-
,
, ,

. ,

. ,
(. . 2, 2.6.1.).
(2=2)2 -
( +) a (
).
-. .
,

-.

(. 2, 2.3) : , 2.
, .. -.
- .
- ,
c , ..
. ()
-, : ( c
c - , ):

19

'

(+')

'

(')

2,

, . -1,3-.

1863

1864

* '

(* +* ')

* '

(* +* ')

- *-
(.. ),
.

) .
(.,
., 1965 ),
. , ( -
) ( )
,
. ,
, .
(2s+2s)- -
25.5.
25.5

'

'
C2

C2

*-*'

AA

*+*'

AS

-'

SA

+'

SS

AA

*-*'

SA

*+*

AS

SS

1864

-'

+'

1865
e
, + (SS) (S). +
.
(+)- ( SS), (+)-, ..
- -. , SS-

. () (S)
.
S- (+), . ,
, .. S .
(+) (S), , ,
, . ,
() () , .. ()-,
.
, 25.5, ,
, ,
. ,
(..
S- S---) .

. ,

, . ,
, S .
.

,
, ,
, . ,
,
. ,
.
. , "
". - ,

, .. . ""
.
. , S- S (. 25.5). , S- S-

1865

1866
, .. , ()
, .
() ().
, , ,
,
(~ 65 /). ,
. (
) :

CH2

CH2

CH2

CH2

CH2

CH2

CH2

CH2

CH2

CH2

CH2

CH2

(2s+2a)-.
(2s+2a)-, 25.6.
: 2,
-- .
,
- , ( ), .
, .. 180 2 . () -,
25.6 ( - ; ),
-.
25.6

C2

C2
C2

S
A

A
S

S
A

1866

1867
25.6 ,
. :
.

S

S
A

A
S

S
A

A
S
S
A

A
S

, .. (
, ).
,
. 25.6 , (2s+2a)
(. . 25.1). (
- ,
).
(2+2a)-.

25.7
25.7

p'
p

C2
2
A
A

A
S
A
S

S
S

2, , ,
-- , . 2
45 -- .

1867

1868
2 ,
( 25.7). ""
,

2, .. -
. 25.7 ,
(2 +2) (..25.1).
2 (2 +2)-
2, 26.7 - ( 2 25.6).
" ", .. (.
25.7)
S
A

S
S
A

C2

S
-

.
,
. 25.2.
. , , - -
- -
, , (..
"" ).
,
, ,

, ,
e .

1868

1869

*' A

A (')
A (+')

*' A

'

(c p
)

S (')

S (+')

25.2

1.
( 25.2.1.).
2. ,
.
3. , ,
. ,
, ,
.
4. ,
,
. 2.

, ,
"" ""
.
5. , ,
,
.
6.
.
: , ,
, .
(4+2)-. ,
( 25.8),
. 25.8.

1869

1870
, ,
. , ,
"" ,
.
34 /; . -,
,
=, .
25.8
A

S
A
S
S

25.9 (4+2s)
(4+2). , ,
, ,
. ,
,
.
25.9.

1870

1871

4a+2s

4a+2a

C2

C2
S

C2
S
S

S
A

A
S

S
A

A
S

(4s+2a),
, .
.
, ,
.
N=4, - N=6. ,
2s + 2s

2s + 2a

2a + 2a

N = 6

4s + 2s

4s + 2a

4a + 2s

4a + 2a

N = 4

, ,
, , .
. .
, .

1871

1872

(4q+2) q = 0,1,2,3... , ,

.
4r , r = 0,1,2,3,.., ,
,

- o .(4q+2) -

(s+)- (4r)- (s+s)- (+)-

. (4q+2)-
, ,

.
(4r)- ,
c, (s+)-.
.
, .
N = 8 (6 + 2)

+ ClSO2N=C=O

C NSO Cl
2

NSO2Cl

( , .. (s+s)- , (s+) ).
N = 8 (4 + 4)

O
NH

HN

HN

4s+4s

NH

(4s+4s ).
N = 10 (6 + 4)

EtOOC N
N COOEt + EtOOC N

N
COOEt
(6s+4s ).

1872

1873

+ O

O
(6s+4s ).
N = 12 (6 + 6)

O
h

O + O

O
(6s+4s ).

25.2.1..


. 1939 . . ,
- .
, -
2, . ,
- - , , ,
-. .

HC
HC

H
C
C
H

CH

HC

CH

HC

H2
C
C
H2

CH
CH

- , ..
-20,
:

20

, ..

(. 25.3.1.).

1873

1874

, (. 12).
, ,
. , -
,
.
. 1971 . .
, ,
. 12, ,
XIX . ., ,
.
,

( 4

2)-

( 2

2)-

.
, , ..
(4s+2s) (2s+2s). ,
. , ,
- (
, 25.3): 1-, 3, 2, 4*.
(i) , ..
2-. (Ni)
, Ni = 2, Ni = 2 Ni. =.4.

*3

Ni = 2

*4

i
Ni = 0

Ni = 2

i
Ni = 4

(2s+2s)- 25.1
(Ni = 0) (Ni = 2):

1874

1875
i

'
i

Ni = 0

Ni = 2

, , .. (4s + 2a), (4a + 2s) (2s + 2a). ,

.
(4s + 2a)-
i
2

i
1

*4

*3

i
Ni = 1

Ni = 3

Ni = 1

Ni = 3

(4a + 2s)-
i
2

i
1

*4

Ni = 1

*3

*
Ni = 3

Ni = 1

i
Ni = 3

(2s + 2a)-

*'

'

, , .
(4a + 2a)-

1875

1876

*3

Ni = 0

*4

*
Ni = 2

Ni = 2

i
Ni = 4

(2a + 2a)-
i
'

*'

*
Ni = 0

Ni = 2

:

( .25.2),
, .
- , ,
. ,
, , ,
.25.2().
( - ), ,
, .
'
()

'
()

'
'

()

BA'
x
3

AB'
2
()

()

()

.25.2. () ()
()

, 1860 -
. -
, -

1876

1877
'A' (.25.2.), , ,
(.25.2.). . ,
, ,
, .. ,
(.25.2 ), , .
-, (.25.2 )
, , ,
.
, .. ,
. , ,
, , (0,2,4,6... ..) ,
, , , 1,3,5,.. ..
, .
, - .
. 12 , ,
4q+2 (q = 0,1,2,3..), .
4r (r = 1,2,3..), ,
. . (4q + 2)-
, (4r)- , , ..

. , (4q+2)
(.. ), (4r) .
. 25.5.
25.3

q = 0,1,2,3...; r = 1,2,3
4q + 2

4r

, .. ,
.
.
.

(2+2)-

, .

1877

1878
4- (.
), .. . (2s+2s)
(2a+2a) 4- (0 2),
..

"

".

, , .. .
(4+2)- 6- ,
, , , ..
, (4s+2s) (4a+2a) ,
(4s+2a) (4a+2s) .

, :
(. 25.2.2), (. 26) ..
:

.
.
25.2.1. , (2s+2s)-
, . 25.10

(2s+2s)-

.
25.10 (. 25.5)

1878

1879
, ,
, .

. ,

.
,
,
.
.
.

, - .
:
,
- ( 25.11).
25.11

, .
, . 12.
, ,
(. 12). ,
,
. .25.3
4 ( - )

1879

1880

()

E = 2

()

E = 3

E = 3

+
+ 3

+ 3

+2

E = 2

()

()

E = 2 2

E = 2

+ 2

.25.3. () , ()
, () () .
,

(). , ..
- + 2 . , .
25.3 , ()
( 2 ) ,

(2),

(2) ,
(2 2 ).
(4+2)- (2+2)-

1880

1881

25.2.2.
-
-, -
n- (n/2-1),
n/2.
,
, -.
,
. ,
.

25.2.2..

:
n/2-1

n/2-1

p-AO

p-AO

- ~90o,
, sp3- .
-
,
, ,
, - .
, . , :

1881

1882

. ,
1,4-2-1,4-b2-
, - -:

a
b

a
b

a
b

a
b

a
()

()

100%
(. 25.1.2).
2,
( -) -,
.
:

2
2

1882

1883
n , n-2 -.
2, - .
,
, (.. ),
. -

, 25.12 (
, - -,
- -).
25.12 , -, , - .
. , ..
.
25.12

A
A

S
S

S
S

A
()

()

,
( 25.13).
.
,

1883

1884
. ,
.

(4q+2)-

(4r)-

(q = 0,1,2,3...; r = 1,2,3 ...).

25.13.

(4q+2)-

. (4r)-
.
, . ,
, 25.1.2. (25.1) 16-
. - 10- (25.2)
- , ,

1884

1885
.
25.5.

25.2.2..
, 25.2.1.,
: .
,
. (
) N=(4q+2),
( ) , N=4r.

.
,

. 25.14

-. ,
, - . N=4
, , , .
-
, - ( 25.15 ).
, .
25.14.
i
Ni=3

Ni=3

i
i

2*

Ni=4

Ni=2

i
1*

i
Ni=1

Ni=1
i

()

Ni=2

i
Ni=0

1

()

25.15

1885

1886

Ni=5

Ni=5

i N =6
i
i

Ni=4

i
i

i
Ni=3

i Ni=4

i
Ni=3

Ni=2
i
i

Ni=2

Ni=1

Ni=0

Ni=1
i

()

()

, .

, ( 25.14) ,
( 25.15) - .

25.3.

, - 1,3-
.
.

25.3.1. -

, .

1886

1887
, (1928 .),
.
-
, ,
-. (4s+2s),
.
(4s+2s)

25.3.1.a.
- . .
:

> = < ()

>=O

()

--

()

>=S

()

>=N

()

-N=N-

()

O=O

( 2)

-N=O

()

-N

()

, ,
O, N .

C N
O

1887

C C

C C

C N

C C

1888

N N

N N
C

C N
C

C
- .

CH3

COOCH3

CH3
COOCH3
COOCH3

150 oC

COOCH3

85%

NC

CN

+
NC

CN
CN
CN
CN

20 oC

CN

+
EtOOC

N
N

COOEt

10 oC

100%

+
O

N COOEt
N COOEt

80 oC

O
45%

CHO
H

, ; ,
.
. , ,
. ,
-

-: -,

1888

1889
.
- , . ,
-1- (VI) , - (VII).

, -
VI .

H
H

R
H

(VI)

R
H

(VII)

, 2 ,
.

H
R

H
H

-, ,
, , ..

, , ,
.

r1

>

>

r2

(r1 < r2 < r3)

r3

-,
. :

>

NH

>

,
. .

1889

1890

S
S +

.
,
. 9,10,
.

O
O
O
+

O
O

25.3.1..

-, , 25.3.1.,
.
,
(. . 2.
RTlnk = const + 2(E1 + E2) + (C1 + C2)

. 2):
(25.4)

k - , E1 E2 -
, C1 C2 -
, (q) o .
2 ,
.
a , b b,
Rab Rab, :

1890

1891

a'

Rab

Ra'b'

C1 =

q a qb
Rab

C2 =

q a ' qb'
Ra 'b '

b'

(
).
, 1 2
1 2.
(.2)
E1 =

(C a C b * ab + C a ' C b ' * a 'b ' ) 2

G1

(25.5)

G1 = ( ) - ( )
E2 =

(C a * C b ab + C a ' * C b ' a 'b ' ) 2

G2

G2 = ( )- ( )
* - , -
, -

. (,
, ..) ,
CaCb* = CaCb*
Ca*Cb = Ca*Cb
ab = ab

E1 + E2 =

a1 a 2
+
G1 G 2

a1 a2 - . , ,
CaCb* = CaCb* Ca*Cb = Ca*Cb
( ). a1 a2
E1 + E2 a(

1
1
+
)
G1 G 2

(25.6)

- .
(25.6), ,

. ,
( 1 2 . 25.4)

1891

1892

.
,
. (25.4) (25.6), ,
,
, .
. (25.6)
.
,
. : , x z.
- , (+), (-) - (, 65, -=2, ..);
x - - , (+)- (, -3, R, -NR2 ..);
z - - , (-)- (,
, N, R ..).
- 1,3-. (. . 1), 10,5 , +1,5 . 9,1 , + 1 .

( = -=2):

,
(. .2).
,
, ( +3 ).
z ,
2=-z .
, ,
25.17.
25.17

1892

1893

x +3

+1,5

c +1

z 0
x -8

c -9

-10,5

z -10,9

. 25.18
1, 25.19 - 2 .
25.18

x +2,5

+1

c +0,5

z -0,5
x -8,5

-8,2

z -9,5

-9,1

25.19

+2,3

+1

+0,7

-0,3

x
c

-8,7
-8,5

-9,1

z
-9,3

, 25.17-25.19
-.
,
(E1) (E2),
.
.

1893

1894

CH2=CH2 (+1,5)

G1

CH2=CH2 (+1,0)

G2

CH2=CH2 (-9,1)

CH2=CH2 (-10,5)
G1 = -10,8 ; G2 = -11,5

G1, G2 .

CH2=CH-x (+3)

G1

CH2=CH-CH=CH2 (+1)
G2

CH2=CH-CH=CH2 (-9,1)

CH2=CH-x (-8)

G1 = -12,1 ; G2 = -9

- z ,
.

CH2=CH-z (~0)

G1

CH2=CH-CH=CH2 (+1)
G2

CH2=CH-CH=CH2 (-9,1)

CH2=CH-z (-10,9)
G1 = -9,1 ; G2 = -11,9

x z ,
.

CH2=CH2 (+1,5)

G1

CH2=CH-CH=CH-x (+2,5)

G2

CH2=CH-CH=CH-x (-8,5)

CH2=CH2 (-10,5)
G1 = -10 ; G2 = -13

1894

1895

CH2=CH2 (+1,5)

G1

CH2=CH-CH=CH-z (-0,5)

G2

CH2=CH-CH=CH-z (-9,5)

CH2=CH2 (-10,5)

G1 = -11 ; G2 = -10

,
, .. , - , ,
, - .

CH2=CH-x (+3)

G1

CH2=CH-CH=CH-z (-0,5)

G2

CH2=CH-CH=CH-z (-9,5)

CH2=CH-x (-8)

G1 = -12,5 ; G2 = -7,5

CH2=CH-z (~0)

G1

CH2=CH-CH=CH-x (+2,5)

G2

CH2=CH-CH=CH-x (-8,5)

CH2=CH-z (-10,9)
G1 = -8,5 ; G2 = -13,4

.
,
- ,
-:

,
. ,
, ..
. , - (..
2, 2.6.1.), ,

1895

1896
. , - , ..

25.3.1..
-

, .
, .. E1 E2 (. 26.4)
.
, . ,
- ( x:) - ( z)
-, , -1,3-,
- , (. 2.4).

, , ,
, ..
.
,
:

, -
, x:,
a ao , x:. -
, - z 21.
(. ),
, , ,
, z.

21

, z (-COR, -COOR, -CN .)

, - (. . 2),
, .

1896

1897

- x: 1
: , ,
, , . .

- z ,
, .
c (-=2, -h ..).

: " " " ",
"-" "-". " ",
, , ,
, .

R
Y

Y
"-"
( )

"-"

"-" .
,
.
-.
1.

, .

25.3.1.,

1897

1898
G1=8,5 (G2=13,4
). G1, ..
( 1 25.4). 2==-x: 2=-z,
:

x
a'
a

b'

a'
a

" "

b'

" "

, ()
,
()
. E ( 25.5)
" "
(CaCb*ab + CaCb*ab)2 (CaCb* + CaCb*)2
" "
(CaCb*ab + CaCb*ab)2 (CaCb* + CaCb*)2
, , Ca > Ca b* > Cb*,
(CaCb* + CaCb*) > (CaCb* + CaCb*)*
, "- -"
, "-"
" ".
2. , .
G1 = 12,5, G2 = 8,5 (. 25.3.1.6), 2, ..
(E2 25.4).
:

z
a'
a

b'

a'
a

" "

b'

" "

, " " , " ".

*

, :(a - Ca)(Cb* - Cb*) > 0, , , ,

.. Ca > Ca Cb* > Cb* .

1898

1899
3. .
, G1 = 9,5 , G2 = 10,4 ( 25.3.1.), ..

G1 G2 , .
, ,
.

z
G1 = 9,5

G1 = 9,5

G2 = 10,4

G2 = 10,4

" "

" "

, - ,
G1 < G2. , " ",
"-", "-" ,
.
4. . G1 = G2 = 11,5
( 25.3.1.), ..
.

x
x

" "

" "

, "
".
, -
" ".
, ,
.

OCH3

OCH3

CHO

CHO
+
*

1899

1900

C6H5

C6H5

C6H5

COOCH3
+

COOCH3
+
*

39

COOCH3

COOCH3

COOCH3
+
*

PhS

PhS

Ph
+

Ph
+
*

+
*

() ()

COO
COO

COOH

COO
COO
+

() ()

COOH

+
*

Ph

COOH
+

COOH

COO

COOH

COOH

COOH

COOH

COOH

COO

,
50% "-", "
" .
" " ,
, ,
. , :

CH3

CH3

CH3
CH3

+
*

+
CH3

*
CH3

1900

1901
, ,
.

25.3.1.. -
, - ,
-. ,
, - (,
).

O
O

O
HH

H
H

( )

- -
:

O
O

O
O

, .25.4.. - -
, ( ) ( =),
,
, . ,
,
-,
.

1901

1902
(VIII)
-.

+
O

(VIII)

( )

( 25.4.), - .
()

.
O

O
O

()
()

()

.25.4. () () () ()

25.3.1.. (4+2)-
(4+2)-
.
. ,
- .
-
(N, O .), :

CN

CN
+

CN

NR2

CN
NR2

(
-40 )

CN
CN
NR2

1902

1903

NMe2

H3C

Me2N
+

H3C
H3C

H3C

H3C

H3C

CH3

NMe2

NC

CN

CH3

NC

CN

CH3

NC
Me2N

CN
CN

H3C
H3C

CN
O
C
CH3

- -40o,
"", ,
.
-
. 1,1--2,2. .
,
.

,
, . , ,
, ,
.
, ,
,
.
:

1903

1904

(-)

(-)

F2=l2

F2=l2

F
F

F
Cl
Cl

Cl
100%

Cl

86%

14%

F
Cl

Cl
Cl
F
F

Cl

,
, ..
. , ,
, -
. - ,
.
, (4+2)-
(
"" )
.
.

25.3.1..
- - ,
-.

, - ,
- , ,
, . ,
- , ,
.

1904

1905

NH
NH

20 oC

N
N

N
N

1,2,3,6-

. ,
.

:

H
H

2
H

- . .
, -
( ). - -
.

1905

1906

H2O2; OH

O
O

O
420 oC

O
O

HN=N - (c. . )
:

EtOOC N

N COOEt

+ EtOOC-N N-COOEt

NH
HN

1.
2. ,
20 oC

+ [HN=NH]

( ) 3,4-.
MeO2CC CCO2Me

CO2Me

400 oC

MeO2C

+
CO2Me

CO2Me

Cl
Cl
MeO2CC CCO2Me

SO2Cl2
Cl2

Cl

- -

1906

Cl
CO2Me
CO2Me

1907

Cl
Cl

CO2Me

Cl +

+
CO2Me

Cl

1,4-

-,

..

, 1,4.

(. 25.2.2.a).
- 1,3 .
.

Ph
+ Ph-C=N-N-Ph
N

Ph
135 oC

Ph

+
N

1,3-
98%

Ph

O
N

+ HC=N-O

~130 oC

90%

-
, -.
, - (2s+2s+2s)-.
2s
2s

(2s+2s+2s)-

2s

,
. , - VIII ,-, IX,
X, ,-- .

1907

1908

CH3

CH3
NH
NH

CH3

N
N

+ N2

CH3

CH3

CH3

VIII

CH3

CH3
H
CH3
N
N
H

CH3
H
N
N
IX

- XI ,-:

CH3

CH3
NH
NH

CH3

N
N

CH3

+ N2

CH3

CH3
XI

, e
, , II -10o,
III - 200. ,
, (2s+2s+2s).

N
XII

-10 oC

+ N2

1,3-

N
XIII

200 oC

+ N2

N
1,5-

o .
,
(. . 24).

1908

1909

N
XIII

25 oC

+ N2

1,4-

25.3.2. 1,3-
4s- - .

2=-2-,
, , (4+2) ,
.

4s

4s

2s

2s

(4s+2s)-a
( 25.20) ( 25.8). ,
, a -,
.
25.20

1909

1910

A
S

S
A
S

O
CH3

O
SAr

CH3

LiN(i-Pr)2

CH3

-78 oC

CH3

R
COOEt

SAr

SAr

CH3
CH3

COOEt
R

, -, - ,
-
.
4 , .
, , 1,3-,
1,3- (., 1958 .). 1,3

1910

1911
,
.

25.3.2.. 1.3-
1,3- - ( in situ) ,
, 4-,
, :

R N N

R N N

1,3- ,
(. 1, 1.11.1)
1,3-. III IV.

H2

N N

H2

XIII

H2

N N

N N
H2

H2

N N
XIV

N N

XV

, , "1,3-" , 1,3-
(III, IV V). ,
, ~6 D) .
1,42 D. ,
.
- 1,3- , .
-,
1,3- ( 1,3- , N O ),
(. 25.3.2.).

1911

1912
1,3- .
.
1,3-, .

1.

N N N

N N N

1,2,3-

2.

3.

N N O

N N O

1,2,3-

4.

5.

1,2,3-

1,2,3-

6.

7.

8.

S
N

9.

1912

1913

10.

11.

1,3-

.
1,3-, in situ

1.

N
C N C

N C

( >CCl=N-CH< )
2.

N
C

C N N

N N

( >CCl=N-NH- + NEt3 2-H-

3.

N
C N

S
R

O
O
4.

N
C

( >CH-N+=C-X NEt3)
5.

1913

1914

( >CH-N+=N-X NEt3)
6.

C
O

7.

1,2- ( )

( )
8.

( a

N N

S
1,3- ,
, .. .
1,3- , ..
, in situ.
1,3-

1.

2.

3.

1914

1915

4.

5.

6.

1,3- . ,
(VI) (VII)
, .

R2

R2
1

R1 N

R N

N O

O
O

XVII

XVI

(VIII) ,
1,3- - ,
=N , . - -
, 1,3- (XIX).
RCH=N-N=CHR
XVIII
1,3-

R
H

H
XIX

1,3-

XIX
:

1915

1916

R CH

RCH N N CHR

N CHR

R CH

CH R

, 1,3-, (
).
: =, , =N, N=N, =O, =S, N=O .. - ,
.
.

Ph
C N
Cl

+ Na
OH

CH(COOEt)2

Ph
H
EtOOC

Ph

C N O
OEt
EtOOC CH C
OH

-NaCl

Ph

O
-H2O

OEt
OH

EtOOC

OEt

3--4--5-

, -,
,
. , :
NEt 20 oC

N NHPh -HCl3
C

Ph

Ph

C N N

Ph

Cl

Ph

S
72%

Ph

Ph-N=S=O

PhC N

Ph2C=S

Ph

Ph
Ph

Ph

Ph

N
72%

N
Ph

Ph

Ph
S
O 87%

25.3.2..
1,3- . 1,3-
. -, 1,3-
,
e - -

1916

1917
. 1,3-
, (4s+2s)-. ,
1,3- ( -;
. 25.3.1.) ,
. 25.3.1.-
-.

1,3-
.

25.3.2.. 1,3-
1,3-,
.
, (,
, ) ,
- .
1,3- . 26.4.
25.4

1,3-

HC N CH2

HC N NH
HC N O

N N CH2

N N NH

N N O

CH2 NH CH2
CH2 NH NH

1917

-7,7

0,9

-9,2

0,1

-11,0

0,5

-9,0

1,8

-11,5

0,1

-12,9

-1,1

-6,9

1,4

-8,6

-0,3

1918

CH2

-9,7

-0,5

-7,1

0,4

-13,5

-2,2

CH2 NH O
O CH2

O O O

, , . 25.4 ,
. 1,3- -
( . 25.4), ,
. , (XX)
- =N 3-. ,
(XXI). . 25.4
"" .

H
H

H C N C

XXI

XX

, ""
(II), , ,
(III).

H C N C

XXIII

XXII

-,

1,3-

. (G1)
, (G2),
G1; G2<<G1,
G2; G2G1, G1, G2 (
25.21).
25.21

1918

1919

G2

G1

G2

G1

G1

G1<<G2
lnk ~ (1/G1)

G2

G1~
~G2
lnk ~ (1/G1+1/G2)

G2<<G1
lnk ~ (1/G2)

1,3- (
= -10,5, = 1,5 ; . 25.3.1.). . 25.4, ,
(G1 = -8,4 , G2 = -11,9 )
() (),
(G1 = -15,0 ; G2 = -8,3 )
() .
, ,
(G1 = -10,7 ;
G2 = -10,6 ).

1,3- R (), x: (-) c (Ph,=2

..) z (-),
, (. 25.3.1.),
G1. , ,
(, z) o (x:, R,
) , G2.
1,3- ,
. ,
-, - ,
.

(. 25.5), G1
G2.

1919

1920

lnk

(RO2C-C C-CO2R ..)

(=-NR2 ..)

.25.5. NN+-N--h
( = -9,5 , = -0,2 )
, ,
1,3-.
, - (z) () ,
.

2N2 > 2N2 >> tN2
, (),
;
1,3- .
(. 25.4),
, .
,
.

-,

1,3-

. (25.4) ( 25.3.1. ).
1,3- , ,
,
o .

. , (-9,3 ) (1,1 )
1,3-. ,

.

1920

1921

25.3.2. . 1,3-

1,3- , ,
,
1,3- . - ,
1,3- ,
. 25.3.1..
1,3-
. 25.5
25.5

1,3- ( (c/)2/15; .
)

HC N NH
HC N O

HC N CH2

N N CH2

N N O

N N NH

CH2 NH CH2
CH2 NH NH

(C1)2 > (C3)2

(C1)2 (C3)2

0,90

1,45

0,92

0,36

0,81

1,24

1,18

0,17

0,85

1,57

0,56

0,66

0,72

1,55

0,76

0,37

0,67

1,33

0,96

0,19

1,28

1,28

0,7

0,73

1,15

1,24

0,87

0,49

1,11

1,06

0,98

0,32

1,29

1,29

0,82

0,82

CH2 NH O

CH2

O CH2

. 25.5 ()2/15, , 1 3 , -
(. . 25.5).
, -, -N -O .
1,3- o -,

1921

1922
-, (25.5) ab ab, ..
(25.6). ()2/15, . 25.5,
1,3-
, .
15 , ()2
.
,

1,3-

.
. G1
( 1,3-) , c
z, .. ( 25.3.1.).
c z
,
(. 25.3.1.),

3- 1-22, .

H2C

5
H2C
4

c (z)

N2
3

c (z)

(R, OR ..)
. G1,
G2.
(. 25.5),
.
, 4- 1-.

H2C

(R) x

(R) x

5
H2C
4

N2
3

G2, 3--4- -1-

22

C 1 .

1922

1923

RCO-CH

RCO

R2N

R2N

, R
,
.
.
G2, - G1.
5-, 4- 1-.

Ph

Ph

Ph

Ph

N
5

N
4

5, . ,
:

Ph

Ph
G2=-9,3

Ph

Ph

1923

N
5

N
4

52%

1924

Ph

Ph
G1=-10

N
5

Ph

N
4

43%

Ph

, G1 G2 .
. -
e , G2,
(. . 25.5) .
.

CH2

N COR

Ph

Ph

N COR

, - ,
, .
,
3- 1--2- ( ).

Ph
N

Ph

O N

N
N
O

c, x, z

O
Ph N

c, x, z

-CO2

O
Ph N

c, x, z

c, x, z

. G2 ( ).
, ,
.
5- :

1924

1925

R N
2

RCH N O

c, x, z

O1
5
4

c, x, z

,
G1 G2,
,
,
.
( z)
G1, .
. ,
1,3-.
, (. 25.5),
5- :

R C

R
3

c, x, z

Ph

Ph

c, x, z

Ph
3
4

c, x, z

O1

Ph
N1
5

c, x, z

G1 (,
z), :

R C

R
3

O1
5

. G1.
,

1925

1926
, . . 25.5
, 4- 1-.

R C

R
R

c (z)

c (z)

.
, ,

1,3- , ,

1,3- .

25.3.2..
25.3.1. - -
,
-2 -3.
.
1,3- ( ),
, ,
- .

,
G2. 1,3-
, - , ,
.

1926

1927

26.3.3.

25.3.3.. e
"" "".
6- e :

(25.7)

- X,
, ,
(4s+2)-. (.. )
:, (2+2+2)-.
, 6- e .

(4s+2a)

(4s+2s)

(4a+2s)

(4a+2a)

-
(4s+2s) (4a+2a), (4s+2a) (4a+2s) .
- ,
(4s+2s).
SO2 RPCl2
( 25.1.1).
, S=O, .. .

),

- :

S
O

0 oC

SO2 +

RSO2H

O 2S

, 6- .
, , = SO2, N2 (.25.7).
:

1927

1928

CH3

SO2 + CH3

CH3

SO2

100%

CH3

SO2 + CH3

CH3

SO2

CH3

100%

CH3

. (XXV)
N-,
N- N-
(Na2N2O3) (NH2F2).
Na2N2O3

CH3

N
H

CH3

CH3

CH3

CH3

CH3

XXV
Na2N2O3

CH3

N
H

CH3

N2 + CH3

()

CH3

Ph

Ph

CO2Me

CO2Me

O +
Ph

Ph

Ph

Ph

Ph

CO2Me

Ph

Ph

-CO2

CO2Me

Ph

CO2Me

Ph

CO2Me
Ph

MeO
Cl

MeO
Cl

Cl
Cl
+ :C(OMe)2

Cl

Cl

Cl
Ph

Ph
Cl

2,3,4,5-

1928

(MeO)2C=C(OMe)2

1929

Me Me
Si Ph
Ph

Ph
Ph
+ (Me2Si)x

Ph

Ph

Ph

Ph
2,3,4,5-

25.3.3.. (2+2+2)
(2+2+2)-

(2s+2s+2s)
(2a+2a+2a). ,
,
, :

NC

CN

NC

CN

80 oC

NC
NC

CN
CN

(2+2+2) -
, , .
:CX2

X = F, Cl

, (2+2+2)-, ,
( 25.3.1.), -
. :

1929

1930

Ph
H

Ph
H

Pb(OAc)4

NH

N
H

Ph
H

Ph

O
N

Ph

N
O

Ph

+ SO2 + N2

N N

N N

Pb(OAc)2

Ph

Ph

+ CO2 + N2
H

Ph

()

Ph

( SO2)

2PhCN + N2

NH2

N-

25.4.

25.4.1. (2+2)
(2+2)-
. 25.2.1,
,
(2s+2), - (2s+2s), (2a+2).
(2s+2) (2+2)
, (2+2)-, ,
- .
, ,
.
h
(2s+2s)

1930

1931

26.4.1.. (2+2)-

, ,
- - .

( = 44 /), ,
( = 19 /).
( -44 /.),

2 ()

. 500 0,01
. ,
.

, .
: ,
(
). ,
-, ,
. ,
, .
.
- (.. ), .

Cl

Cl
Cl

F
F

Cl

Cl

Cl F

Cl

Cl

Cl

Cl

Cl
Ph

Ph
Cl

Cl

Ph
F

Cl
F

Cl

Cl F

Cl

F
Cl F

1,1--2,2- ,
(2+2)-.

1931

1932

Cl

Cl

Cl
Cl

XXIV

Cl
Cl F

Cl F

Cl

Cl
F

XXV

Cl

Cl

XXVI

Cl

. - , , IV,
V VI. XXIV 8 /
V 21 / XXVI.
,
- .
(2+2)- ,
--. :

Cl

Cl

CH3
H
CH3

+
F

CH3

CH3

Cl

Cl

CH3

CH3

Cl

Cl
Cl
CH3

Cl

+
CH3

F
F

25.4.1.. (2+2)-

(2+2)-

1932

1933

, ,
.
, , ,
.
,
, N, F3, O2R, SO2R, NO2 ..
(+)-, , R ( ), RS ( ), NR2 () ..

=-z ,
- =b - .

X:

X:

(2+2)-

X:

X:

Z
Z

a=b
X:

X:
H

b
Z

(2+2)-

OMe
NMe2

H3C

H3C

+ CH2=CHCO2Me
NMe2
Me2N CO
2
H

H3C

H
H3C H

1933

H
H3C

CH3

1934

.
.
,
, .

CO2Me
N

SMe + MeO2CC CCO2Me

N

Me

Me

CO2Me
SMe

CO 2Me
CO2Me
N

SMe

Me

(2+2)-, , ,
.
,
-:

X:

:X

1934

-1-

1935

Et

OEt

CN

Et
NC
NC

-1-

NC

NC

OEt

CN

CN

Et

CN

CN

OEt

Et

NC
NC

CN

CN
CN

XXVII
98%
( )

OEt

Et
NC
NC

OEt

NC
NC

CN
CN

XXVIII
2%
( )

VII. - VIII.
VIII 2%. ""
(7% 2Cl2, 10% , 18%
3N); ,
, ,
.

26.4.1.. (2+2)-
, , ,
, a - (.
. 7). ( ) ,
.

H
H
H

(2+2)-.

(2+2)-, (2+4)-
- .

1935

1936

O
+ R2C=C=O

R
R

(2s+2s)- ,
(2s+2)- , ,
: , .
,

(, 1969).
.
1) .

2) (H 9-10 /),
(S 40 /.),
(. . 3).
3) . ,

50 , --
( ) - 63000 .
4) -
, .
7
6
5

1
4

2
3

+ R2C=C=O

7
1

2
5

7
3

,
(2s+2a)-.

-
- .
R2=+-O-,
-: ( =) ,

1936

1937
"" ( ). -
, (2s+0s), . - ,
o .
,
"" (2s+0s)- (2s+2a)-.
(2+2)- .
.

(2+2+2)-

- . ,
= - - - - -. -
, - -
, .. .

.

3
2

- -
.
=O
()

(3,8 )

(-12,4 )

.
, , ,

1937

1938
,
( 25.3.1.).

R'

R'

C C O

R'

R'

(R, R' = Alk, Ar, OAlk)

R CH CH2

" ",
.
-, , .

R
R

R
C C O

O C C

O
+

H2C

H2C C O

O
R

H2C C O

O
O

,
. 25.6
25.6

R2C=C=O

R2C=C=O

O=C=C=C=O

R2C=S(O)=O

R2C=C=NR

RN=C=O

R2C=C=S

RN=C=S

R2C=C=CR2

O=N=O

O=C=O

RN=S=O

S=C=S

RN=S(O)=O

RN=C=NR

,
.
. - e ,

- .
,
. , ( a) -

1938

1939
, a .
,
"".

H3C

C C=O +

CH3

N CH C

H3C

(H3)2==O

H3C
H3C

H3C
H3C

CH3
N

O
CH3

CH3

PhCH

Me

Me
N

Ph2C=C=O

H3C

H3C

CH3

PhCH

Ph CH N Me
+

H3C
H3C
H3C
H3C

CH3

Ph2C

CPh2

Ph2C=C=O

Ph

Me

Ph

Ph
N

Ph

Ph
O

Ph

Me

Ph
Ph

Ph CH N
+
Ph2C=C=O

Ph

PhCH

Ph

Ph

Ph
N

N
Ph
Ph2C

Ph

ROH

Ph
RO CH N
Ph2C

1939

Ph
O

1940

R N C N
+

Ph2C

Ph

Ph2C=C=O

Ph

RN

N
R

HOH

O
Ph2C

C N

RNH

R
O

, (2s+2a)-e
, *- ,
, .
(2+2)- " ".
, , .

H2C

C CH2

H2C

C CH2

25. 4.1.. (2+2)-

(2+2)- .
,
.

:CH2 ()

:NR ()

(. 5).
,
, , -
. ,
,

(. . 27). ,

1940

1941

R C CH=N=N
O

- N2

..
R C CH

O=C=CHR

C(O)R
+ N2

RCOCH=N=N + Cu + >C=C<

,
.
. , ..
, . 25.7.
25.7

:CH2

:CX2 (X = F, Cl, Br)

:CHCOOR

:C=CR2

:CAr2

:CArX

( )

:C:

..

..

NCOR
NCN

..

NNR2

. 5,
,
. .
, (.5, 5.5.2).
, R (F, l, r, OR, NR2
..), .

, .

CH2

+ H2C CH2

H2C

CH2

CH2

,
, .

1941

1942
, , ,
.
.
.
, ,

..

, , :l2, :F2, NNR2.

.
(2+2)-
(2+2), :

25.4.2. (2+2)-
(2+2)- .
,
, .
, , ,
(~ 10-9 ) , .
( ) ,
, ,
.
, ,
.
. Ph2C=O.

(2s+2s). ,
. o.
.

(2s+2s)-

e
, - -2-.

1942

1943

H3C

CH3 CH3
CH3 CH3

H3C
h

+
H3C

CH3
CH3

CH3
CH3

H3C

H3C

+
CH3

CH3
CH3

CH3 CH3

H3C

CH3

CH3

CH3

CH3 CH3

, , -,
. ,
,
.

h
Ph2CO

Ph

Ph

Ph
h

Ph

1-[2.2.1]
h

, .

O
O

1943

1944

O
h

.
,
. .

O
h

O
O
O
O

Br
-

O
Br

COOH
O

Br

Br

HOOC
O

. ,
,
, .

O
CH3

HN
O

O
CH3 CH3

HN
O

N
H

NH
N
H

N
H

, :

CH3

O
Ph

+
CH3

CH3

Ph

CH3
CH3

2--3,3,4
( )

1944

CH3

CH3

+
Ph

CH3
CH3

2--3,4,4

1945

O
h

O
-

-, .

(n*) - .

,
. .
I
(), "
" . - ,
.
,
3.

On
O

XXIX

XXXI

XXX

(.
).
, , ,
XXX XXXI, .
: , -, :

?
,
, ,
(. . 2, 2.2),
.

1945

1946
,

2- II,
III. ,
(n*)- *- ,
(IV).
h

XXXII

()

()

O
XXXIII

XXXIV

-
, (n*)-
, .

, , , -,

V.

R
O
Ph

R
h

+
H

Ph

H
Ph

O
R

XXXV

25.5.
25.2.2;
- ,

, ,
. -,
, .

1946

1947

25.5.1.

, .

, ..
. ,
, .
2,3-.
,- , -l,

- - ( " "
" ", . 25.4.2)

CH3
CH3
CH3

CH3

Cl

Nu

CH3

(-)

CHNu

(-)

CH3

CH3

CH3

H
H
H

Nu

H
H
CHNu

(-)

CH3

(-)

CH3

, -, ..
.
,- -.

CH3
CH3

CH3

CH3

H
H
H

Cl

Nu

H
H
CHNu

CH3

CH3

, - - - -.

1947

(-)

1948

CH3

CH3

H
H

Nu

CH3
H +

CH3
CH3

Cl

CH3

CHNu

CHNu

CH3

CH3

(-)

(-)

,
- , -
. 1967 . , ,
.
, -
(.25.5). , , ..
SN1. SN2-,
-.
.
- ,
.
.
.

Cl
Cl

Cl
OMe

OMe
+ :CCl2

O
2--4,5-
(13%)

Me

Me X

Me
Me

X
Me

:CX2
(X=Hal)

-X

Me

Me

-H

Me
Me
1,2,4--3-

1,2,3-

( 2 l t,
).

Cl
120 oC

:CHCl

1948

1949

Cl
Cl
440 oC

:CCl2

:CCl2

CaO

63%

Cl
Cl 140 oC

Cl
3-

Cl

:CHCl

H
CH3

CH3

,
- - .

Br
+

:CHBr

-2--1-

Ag
H2O/

NaHCO3
H2O/

OH
+

Ag
H2O/

-2--1-

OH

Br
Br

:CBr2

150 oC

Br
Br

,-

AgClO4
MeOH

H
H
OMe
Br

,-

1949

1950
-,
- -. , g+
SN1-, . r . " " " "
, -,
" ".

H2O
-

+Ag
-AgBr

OH

Br

H2O

OH

SN2- (. . 25.5),
-.
H2O

+
Br

OH

, .
,
.

Br
Br

:CBr2

150 oC

Br

LiAlH4

Br
Br

1. Me3CLi
2. MeSSMe

SMe HOAc

TiCl4

1950

1951

Br

Br
Br

OMe

Ag
SMe MeOH

1. Me3CLi
2. MeSSMe

SMe

MeS
MeSH
CF3COOH

SMe

H2O
CF3COOH

25.5.2.

25.5.2..

(. 25.2.2).

.

,-2,3-

COOR
Ph
Ph

1. i-Pr2NLi;
; 0 oC
2. MeOH;
-78 oC

COOR
CH2Ph

Ph

94%

COOR
+

CH2Ph
Ph

6%

,
, ,
.
,
:

COOR

COOR

CCOOR
100 oC

N Ar
COOR

N Ar
COOR

1951

ROOC

CCOOR

COOR
N Ar

ROOC

COOR

1952

COOR

COOR
ROOC COOR

CCOOR

100 oC

N Ar

CCOOR

COOR

ROOC

N Ar

ROOC

N Ar

ROOC

()
:

C:

( 1958 ).
:

R1
R1R2C=CR3R4 + :CBr2

R1
-LiBr

R2
Br

R3
R4

R2

R3
R4

MeLi
-MeBr

R1

R3
R4

R2

Br

Li

Br

R1R2C=C=CR3R4

30 90%.
.
MeLi

0 oC

CH3

CH3
Br

CH3-CH=C=CH-CH3

80%

2,3-

Br

C7H15

CH3

CH3-CH=C=CH-C7H15 81%
Br

2,3-

Br
CH3

(CH3)2

CH3
Br

CH3Li
-78 oC

(CH3)2C=C==C(CH3)2
2,6--2,3,4-

Br
Br
Br

BuLi
-95 oC

81%
1,2-

1952

50%

1953

25.5.2..

(- (.

. 26)).

(25.8)

, - .
(28,5 /)
, . (25.8) .
1905 .,
, ,
(25.8). , .
1950- ,
, .
= 32,5 /, S0,
(. .

. 3).

.
, -3,4- ,-1,4 , - - ,-
,-1,4- .

b
b
a

a ,

. -3,4-
,-.
, ,
.

1953

1954

COOMe
Ph
Ph

COOMe

Ph

130 oC

Ph

COOMe
COOMe

+
Ph

COOMe

Ph
COOMe
78%

24%

, 3-, 3,4-, 3,3,4 3,3,4,4- ,

. -3,4 ,
99,995% .
.

CH3

CH3
CH3

175 oC

CH3
CH3

+
CH3

99,995%

0,005%

, 0,005% ,-2,4-,
, S 0
H 11 / ( ).
, ""
, 3,4. ""
"" (. 25.2.1).
(
) -[n,2,0],
- . ,

, n. .


. ,
300o.
3 4
, .

. , ,
, -.

1954

1955
, , , ,
48o:

F
F

48 o

F
F

,
. 700oC
, 10% .

F
F

700 oC

F
F

F
F

10%

,
, (
o ; = 35,4 /).
, (25.8) ,
. -,-
, .

COOMe
Ph

Ph

Ph

Ph

COOMe

Ph
Ph

COOMe

COOMe
COOMe

COOMe
Ph
Ph
Ph

Ph
Ph
Ph

1955

1956
""

, .
-[n.2.0]- , (n+4)-
. n , (n+4)- , .

(CH2)n

(CH2)n
,-

-[n.2.0]

[n.2.0] 20
. , n4,
- .
. (1) ""
. (2) ""
, -
- . (3) ,
,
--:

, n.
n =1,2,3,4 n5.
(1). 2- [2.1.0] (n=1). 2-[2.1.0] -
, 1965 . -.
.
2

1
5

CCl4
25 oC

1
5

= 26,9 / S = 6 /..
- ,
, .. . ,
.
,
(1)-(4). ,
: " "
(. 25.9), , ,

1956

1957
. -
"" . (27,1 /)
.
(2). 2-[2.2.0] (n = 2). 2-[2.2.0] 1967 .
, ,
48 , 130 , 330o

2-[2.2.0]

1,3-

,-, ,-

. , , -,
, .. , .
, , 3,7[4.2.0.02,5].

+
3,7-[4.2.0.02,5]

, , ,
, , -

, . ,
.
-
. 2,5-[2.2.0] ( )
2 , 90 30 .

But

2,5-[2.2.0]
( )

But

XXXVI

But

. , 1,2,5---[2.2.0]
(XXXVI) 15 200o.

1957

1958
(3).

(n=3).

6-[3.2.0]

6-

[3.2.0]
300-400.

CH3

CH3

400 oC

CH3

CH3

17%

6-[3.2.0]

(4)

7-[4.2.0]

(n

4).

,-1,3-

, 7-[4.2.0]
"" .

k1
k-1
7-[4.2.0]

, -1,3-

, ,-
: k1 H = 32,6 / S = 0,
k-1 H = 26,9 / S = -1 /. 250
,-1,3- 1,5- ,-:

k1

k2

k-1

,-

(5) [n.2.0] n 5. ,
, - ,

. .
250 oC

Me
Me

Me

Me
330 oC

Me
Me
Me

Me

1958

1959

Me
180 oC

Me

Me
Me

140 oC

200 oC

, n 1 6 . n = 13 "a " (.26.9). n

=4 ,
- ,-. ,
n = 5 , -

.


, -, b,
:

R
a
b

R'

R'

C
C

R
R'

- (XXXVII)
-.
X

X
Y

(XXXVII)

1959

1960

Me

COOMe

Me

COOMe

NMe2

COOMe

Me2N

COOMe

COOMe

NMe2

. HCl

OH

Me2C

C CH2COOH

COOH
CH2
C
EtO

COOMe

Me

Me

CH

Me

Me

COOMe
+

EtO

OEt

OEt

Me
MeCO CH C

90 oC

Me

COOMe
EtO

COOMe

COOMe
OEt

N
-3-(N-)5-

COOMe
COOMe

COOMe
OEt +

COOMe

NH

NH

COOMe
COOMe
NH

OEt

1960

OEt

2--3,4-5,6-

1961

Me

Me
h

COOMe

200 oC

COOMe
Me

Me
COOMe

COOMe

COOMe

COOMe
1--3,4-

O
O

MeO

MeO
O

MeO
, (, , , )
,
-, - .

CF3
(F3)2C=O + HC

C OEt

CF3 70 oC CF3

O
EtO

C CH COOEt

CF3

2--4,4--2-

O
CH
CH CHMe
O

Me
Me
Me

1961

1962

Ph

Ar

Ar

PhC CNEt2 + ArC=NTs

Ph

N
Et2N

H
NTs

Et2N

Ts

Ar = Ph,

O
N

25 oC

Ph

O
Ph

N
Ph
EtOOC

Me2S=NAr + EtOOC

C C COOEt

COOEt

Me S N
Ar

Me
EtOOC

COOEt

EtOOC

COOEt

Me2S

NAr

EtOOC

COOEt

Ar

Ar = n-ClC6H4, n-NO2C6H4

25.5.3.

.
1,3-,
(=, =, =NR ..), ,
:

C N N

3-

N
C N N
N-

1962

1963

C O
C N

- , .

Ph

[PhN N N N N]

N N + N3

PhN3 + N2

Ph

N N

.
1964 .

1,3,5-

1,4-

25.5.3..
( 25.2.2)

, :

Ph

Ph

Ph

Ph
Ph

Ph
Ph

Ph

Ph
Ph
Ph

()

1963

Ph

1964

Me

Me
Me

O Me

Me

275 oC
1

Me
O

COOH
COOH
COOH

Ac2O

COOH

O
2,4-[4.2.0]-1,6

"" ,

.

XXXVIII

-15,16-

(XXXIX).

Me
Me

50 oC

XXXVIII

Me
Me
XXXIX

25.5.3..
,
,
( 25.2.2.).

"" (25-30 /),
7 /,
. ,
( )
,
.

1964

1965

,
.
k1 = 0,25
-85 oC
1,3,5-

(2,4-[4.1.0]

.
. 26.

.
,
2

,
2

CN
CN

R = 1-, 2-, 3-

R = Alk, Ph

Ph

Ph
Ph

Ph

Ph
Ph
F

F
F
F

F
F
H O Me
O

Me

7.
(N, R .) ,

1965

1966
(r, =), (.
. 2).
.
, S~0. ,
,
- .

25.5.4..

(N, O, S ..),
. .
(1). -

O
(2) -

2-

OH

(3) 1-, 2- 3-

+ Nu:

1-

Nu

Nu
Me

Me

CH2R

CH2R

Pr

Pr
Et

Et

Et

Et
N

3-

(4)

1966

1967

R
N
N

R
.NH3

+ KNH2
Y

H2N

N
N

(Y = Br, OMe)

R
N

N
N

NH

-Y

C
NH2 N

H2N

N
N

NH2

Y
N
H

NH

Y
N
H

. ANRORC-
15,
. ANRORC- ( ),

. (
) ,
.

25.5.4..

, , .
(,
). , ,
, , -.
,
, NRORC-
(. . 15), .

1967

1968
,
.

R2

R2
R1

+ NH3
R1

+ H
R1

HO

R1

R2

R1

R2
R1

NH OH

R1

R1

NH2 O

R2

R2
R1

R1

N
H

OH

+ H2O

R1

R1

O
OH

C
CH

NH C CHCOOEt

4-

PhCOCH3 + (EtO)2CHCH=CHNMe2

PhCO(CH=CH)2NMe2
Me2SO4
Me2NH

81%

NH3

Ph

NH4+

1968

Ph
Me2N

CH

CH
2

NMe2

1969

+ NH3
O

OH
O

-H2O

HO

OH HN

OH

R2

R2

R2
+ NaS
O

OH

R1

OH

O H2N

NH2

R3
O

R1

R3

R1

R2

R2
+

R1

R3

R1
O

R3

R3

NMe2
Cl
+

N
Me2N

NMe2

NH2

NMe2

N
90%

NMe2

NH2

+ NH2
Br

2-

H
C NH

.
NH3

Br

N
R

1969

CH3

C CH2

1970

NH2
N
N

.
NH3

+ NH2
Cl

H
N

Cl
N

C NH
N

C CH2

N
N

CH3

2--1,3,5-

25.5.4.
, -, ,
, ,
. ,
, . , ,
", , ",
,
. (4q+2)-
, 4r-e - .

,
. , ,
, , ,
.
,
:

R
(CH2)n

(CH2)n
R

, n,
, ,
,
.

[2.1.0], , ,

1970

1971
2 (, ,
).
h
EtOH

, ,
, - ,
, .

R
R

R
R

(L)

(LI):

Fe(CO)5
-CO2
-2CO

Fe(CO)3

(XL)

(XLI)

6- , ..
. , ()- (LII)
-9,10-, -9,10-.

(XLII)

1971

1972

26

26.1. 1975
26.2. 1977
26.3. 1981
26.3.1. [1.2]-O 1981
26.3.1.a. 1981
26.3.1.. 1984
26.3.1.. 1987
26.3.1.. 1987
26.3.1..
1990
26.3.2. [1,J]- 1993
26.3.2.. [1,3]- 1993
26.3.2.. [1,5]- [1,7]- 1996
26.3.2.. [1,4]- 2002
26.3.2.. [3,3] - 2003

26.4.
2006
26.4.1. - 2006
26.4.1.. 2010
26.4.1.. . 2012
26.4.2. 2019
26.4.. 2027
26.4.4. 2029
26.4.5. 2031
26.4.5.a. 2032
26.4.5.. 2033
26.4.5.. , 2034
26.4.5. 2034
26.4.5. . 2036
26.4.6. 2037

26.5.
2038
26.5.1. 2039
26.5.2. 2040
26.5.3. 2041
26.5.4. 2042
26.5.5. 2043
26.5.6. N- 2044

26.6. 2045
26.6.1. 2046
26.6.2. - 2046

26.7. 1,2- 2048

26.7.1. 2049
26.7.2. 2052
26.7.3.
2053

26.8. 2054
26.8.1. 2054
26.8.2. 2056

1972

1973
26.8.3. 2061

26.9. - 2062
26.9.1. O 2062
26.9.2. 2065
26.9.3. [3.3]- 2069
26.9.4. 2072
26.9.5. 2075

26.10. 2077
26.10.1. 1,2- 2078
26.10.2. 1,2- 2079
26.10.3. 1,5- 2079

26.11. 2081

( W)
, .
W

W
A

, -
.

, , ,
-2- -=. W
(, W = r) o (W = Alk, r).
o ,
,
.
1

CH2-CH=CD2

CD2-CH=CH2

B
:

. W

, .. W

1973

1974

N-

:
Cl

HCl

NHCOCH3

NHCOCH3 +

Cl

COCH3

Cl

( ,

- -:
C6H5NClCOCH3 + HCl

C6H5NHCOCH3 + Cl2

(H2O)

(H2O)

(-, -) ClC6H4NHCOCH3 + HCl

,
. , ,
,
-,

:
Ar

Ar

+ 2H

N N

N N
OH2

H
Ar

N N

OH2

Ar

N N
OH

Ar

N N

OH

- ,
-, -:

1974

1975

N N

N N
OH

OH

,
.
.
, : (1)
, (2) - , (3)
.

, .

26.1.
W
-, .. - W-B,

- W-A.

W :
W

W
A

B
(I)

B
(II)

. I II
: II W
W , I, .
, II
, I .
( ), ..

1975

1976

. , II ,
I. ,
,
.

II. ,
1,2- :
R

C C

(R = H, Alk)

(26.1)

C C

+1/2

+1/2

( ):
W

W
1

CH2 CH CH2

CH2

CH

CH2

CH2 CH CH2

CH2

CH

CH2

(A)

CH2 CH CH2 (26.2)

CH2 CH CH2
(A)

(B)

(B)

,
.

(CH=).
.
( )
,
, (
).
"" 8-11- (.
26.3.1.).

1976

1977

(B)

(B)

D(W)

(A)

D(W)

(A)

(26.3)

OH

OH

OH

CH3

CH3

CH3

I,

-,

1,5-

(. 26.10.3 )
5O

1
2

(26.4)

26.2.

: -, (.
I II) , -,
(,
).

( II),
.
By- .
, i j
[i,j].
-,
-.

1,

i j.
:
[i,j]- , -
1,1 i,j.

1977

1978

(26.1) [1,2] , o (26.2) - [3,3]-

.
+

1C

C1
C 1 C2

1C 2C

[1,2]-

2
1

1
2

-
( 26.1)

2
3

3
2

( 26.2)
[3,3]-

[1,3]:
1

[1,3]-

3
2

a (III) [1,5]-
1 C5:
5

5
4

1
3

4
3

(III)

1
2

(IV)

(IV)
- 1-1 - ( 6 )
.

:
1. ,
.

1978

1979

W
A

(. 26.1),
, .
,

. ,
(, ).

( 26.4.4), ( 26.5.1) , (. ).
. 2.
.
W

W
A

,
( 26.8) .
,
-.
3. .
W

W
A

1,2-
, 3,3,3- Br2
.

1979

1980

Cl

Cl
Cl

Br

C CH CH2

Cl

Br

C CH CH2
Cl

Cl
Cl Br
Cl

C CH CH2
Cl

Br2

Br2

Br Cl Br
Cl

Cl Br Br

C CH CH2
Cl

Cl

C CH CH2
Cl

53%

47%

1,2- ,
1,5- ( 26.4),
.
4. -
1-3 ,
; , ,
. , ,

"" , . B

, ,

(.

26.3.1.).

(
).
-

. ,
,

. -
.
, .. - , ,
, .

1980

1981

oe
( ) K ( ):
R

6 -

5 -

R
R

5 -

(
)

(
)

R
5 -

,
.
26.9.5.

26.3.
,
,
.
[1,2]-
, .

26.3.1. [1.2]-o

26.3.1.a.

, 1,2 . 1,2-
. 1,2. ( 26.10.1). 1,2 , lk r
, , ()
.

1981

1982

,

, , .e. ,
. 1,2-

- .
W
A

B
W

W
A

, (
).
, ( )

(
), (
).
- , W- .
H1s, C2p (
o ) spx - ,
( x 3,
x = 0, 3 > > 0).

:

1982

1983

H1s
Csp3

H1s

C2p

C2p

Csp3

()
(
):
i

.
(Hu)

(M), ..
:
i

i
..
(Mo)

i
3

i
1

,
.
-

, 1,2-
( 25):

1983

1984

. , ,
(. 26.8).
,
1,2-
, , 1--.
180 ,
0
.
H

H
H

H
H

, 2, , sp3- ,
, ,
, :

26.3.1..

1,2-
:
,

1,2-

: - -
-
- - -
. 26.1.
1984

1985

26.1
(A=B=C;W= )
-

2e

Hu

(==; W = )
+

Mo

, ,
R e s-, 2 - Csp3-.
,
26.2.
26.2
(==W=)
-

(1)

(2)

(V)
Hu

(3)
+

(4)

(VI)
Hu

(A=B=W=C)

1985

1986

(1)

(VII)

(2)

Mo

(3)
+

(VIII)

(4)

Mo

, 26.2,
(VI) (VII) -

(V),

-
(VIII). :

,

.

R1

R2
C*

R3

C C

R1

R2
C* R3

C C

(. ).
26.2 ( VIII),

. .
,
. ,
VIII -
, .
VIII ,
, e 26.8.

1986

1987

26.3.1..

-,
,
. 1,2-
,

, :

C C

C C

(26.5)

C C

(26.6)

C C

C C

C C

(26.7)

,
,

(,

) , .

. ,
, ,
26.4.1..

26.3.1..

1,2-
( ), .

1987

1988

. ,
, , 1,3- (.
26.4.1.). ,
. ,
1,5- , CH3 (. . 26.3). .
1,3- - ..
.. I960 .
14

CH3 CH2CH2 NH2.HClO4

14

CH2 CH2CH2

H
14
CH2CH2 CH2

HNO2

1,314

HOCH2 CH2 CH3

(~1,5%)

, 13 -
1,2-.
CH3CH2CH2

1,2-

CH3CHCH3

1,2-

CH2CH2CH3

, 1,2- ,
.
2--1- (IX) 1,2% 3-1-, (X)
1,3-, 1,2-. 2-2- 3--1- . , (X)
IX 1,3-.
CH3
CH3
CH3CH2CHCH2OH

CH3

1,2-

CH3CH2CHCH2

IX

CH3CH2CCH3 1,21,3-

CH3

CH3CHCHCH3
X

CH3
CH2=CHCHCH3
1,3-
XI, II.

1988

1989

H
CH2

CH2 (XI)

CH2

CH2 (XII)
CH2

CH2

C2- XI

, 1,3-

, 1,5- ( 26.3)
- [1,2]

( ""
, .. XI,
. 26.3). ,

"",
. , 1,8- 1,5

[1,2]-c

[1,2]-

).
II
- , XI
. ,

, ().

. ,
()

--

(V),

1,2- .

(IV), 1,2-.

1989

1990

CH3CH3
CH3

CH3

C CH CH3

CH3

CH3

XIII

CH3

3
H
CH2 CH3
2

CH3 CH2 CH3

1

CH3

XIV

C CH2CH2CH3
XV

26.3.1..

II

XI.

(,

).
(,
..), .

, .

, W ,
-, Y- (
, ),
1990

1991

XVI, VII XVIII.

W
A

(XVI)

:Y

B
X

(XVII)
S N1

W
A B

A B
Y

Y (XVIII)

( - W = Ar

VI

(.

25. ). , VI
VII

II, VI VII
(. 26.3.1.6).

W--- ,
, .
, W--+

, II VIII.

,

-+ . ,
.
,
.
1991

1992

W-A-B-X , W X

.
W X , .

R1

R1

R1

W
(c)

- X-

R2

R2

R2

R2

R1

R1

R2
R2

++

R1

()

W-A-B+ , ""
, X-
W. SN2-,
W (.. - -W).
(.
VI VII).

, W
+W,
(
+-). A+-B-W ,

Y-.

, .. Y- W
SN2 ( VII VIII).

26.1;

1992

1993

26.4 26.5.

26.3.2. [1,j]-

26.3.2.. [1,3]-
26.3.1. , 1,3-
[1,2]-
.
26.1

W-A-B-X + - -A-B-W
-
*
W-AB

- -W

. * - , " "
, ,
, .

[1,3]-

.
1

[1,3]-

W
3

1
2

, ,
( - -), .. ,
,

).

1993

1994

(W=)

- - - =
:
-

- H

, ,
, .
, 1s
, (
). , [1,2]-c
(. 26.3.1.a)
,
, , ,
, .
[1,3]-c .

[1,3]-,

. ,
:

R
h
[1,3]-

AcO

H
AcO

[1,3]- .
:

1994

1995

(2s + 2a)

(2a + 2s)

,
,

,
. ,
,

[1,3]-c

d
C
CH2 CH CH2

CH2

a
C
bd
CH

a
C
CH2 CHCH2

CH2

d
b

()

, ,
:
H
2

Me

=36 /

Me

O
1

).

1,3-

Ph
Me

NC

Ph
NC
NC

Me

250 o

1995

H
Me

NC
Me

1996

XIX,
,

(
).

Me

Ph

CN

(XIX)

NC

Me

CN,
- . , -
, -
.

26.8.2.

[1,3]-

(. 26.11)

26.3.2.. [1,5]- [1,7]-

[1,5]- .
W

By-
(.25), [1,5]-
, :

1996

1997

H
H

[1,5]-

[1,5]-

[1,5]- . [1,5]-
[1,3]-. ,
[1,3]- ,
[1,5]- .
[1,5]-
e 30 /.
. , 1,3-
kH/kD = 5,
.
c

XX R,Z- S,E XXI:

H
Me

Me
Et XX

Me
Et

[1,5]~H

Et D

Me

Me R,Z-XXI

Me

[1,5]~H

Me
D
Me H

D
Et

S,E-XXI

, , ,
S,Z- R,E-:
H
Me

Me

Me
Et XX

Et D H

Me S,Z-XXI

1997

1998

H
Me
Et

Me

Me

D
Me

D
Et

R,E-XXI

, , ..
.
, - ,
. [1,5]-
,
( ). 10 /.
H
2

D
5

[1,5]~D
200 oC

H
1

[1,5]~H

200 oC

[1,3]- ,
"" :
H

[1,3]~D

2
3

[1,5]- ,
.
CH2
CH

[1,5]~H

CH2

2--1-

1,4-

=
, , ,-
(.. ) ,:

1998

1999

MeO

H2C

MeO

C
CH

CMe2

CH

MeO

CH

CH

CMe2

CH

H
CMe2

[1,5]- ,
. :
,
-,
, .
.
a

b
c

bc

b
a

,
, [1,5]-

:
Me

Me
2

Me

Me
1

[1,5]Alk

4
5

H
Me

[1,5]H

Me

Me

Me
[1,5]Alk

Me

Me
[1,5]H

H
Me

1999

Me

2000

[1,5]-
.
[1,5]-:
Me
2
3

X
1

Me
1

Me

Me

CHO > COCH3 > H > =2 > COOCH3 > CN >CH3

, , ,
( [1,5]- 20
/ , 3).
(CH3)3Sn, (3)3Si, r NO2. ,

(. . 25), .
.

(C) .

, , ,
.

()+

. C5H5-
(. . 2),
- .
( 26.3).
26.3

2000

2001

H
-

+
()

O
C1

O
C

*- ()+

-
55

-
3

55

[1,7]-

.

[1,3]-
. , :
H

CH3

HO

HO

[1,7]-
. ,
.
[1,7]- ,


,

:
i

[1,7]- :

2001

2002

CH3

CH3

CN

CN

7
6

1
2

5
3

[1,7]

CH3

CH3

, [1,7], ,
, ,
.
[1,9]- :
Me

Me
2

8
7

Me

N
N

Ph

Me
N

[1,9]~Me

Ph
N

, . .
,
. ,
, [i,j]-.

26.3.2.. [1,4]-

[1,3], [1,5], [1,7] .. ,

-
, . [1,2],
[1,4], [1,6] .. . [i,j]-
; , , ,
, ,
.
[1,4]- ,
- .

2002

2003

:
Me
HO
Me

Pr

4
3

Me
Me

Pr
[1,4] HO

Me

Me

Me

( )

Me

Me
[1,4]

N
O

O
R

( R)

O R

26.2

[i,j]- ,
,

. ,

(. 26.7).

26.3.2.. [3,3] -

[3,3]-
, .

2003

2004

(. 26.2),
1,5- 300 .
,
-.
2

2
1

3
2

- ,

,
e -:
-
( )
-

26.2

[1,j]-

W
j-1

j-1

[1,2]

[1,4]

[1,3]

[1,2]

a
s

[1,6]

[1,5]

[1,4]

a
s

2004

+
+

2005
: - , - ; s -, -
; "+" - , "-" , "" .

.
.

3
2

1
.

26.1.

.26.1
. ,
1, 2 3
- .
, , .
(s,s),
(II), (III).
(,),

(IV).

(s,a)-

(XXV) , ..
,
, .. .
(s,s)

XXII

(s,s)

XXIII

2005

(a,a)

(a,a)

XXIV

XXV

2006

IV , ..
. II
III , . c
II , III
-
( II-V ).
99%
(II), 1,5-, ,
(. 26.8.9).

26.4.

26.4.1. -

- 1899 . .
( )
. 1920- ,
.
CH3

CH3
CH3
OH

OH2

()

CH2

CH2

-H

()

( )

,
.

2006

2007

: H2O, Hal-, TsO- ..,

, :
-

(H3)2C-CH2-OH

Br
H

(CH3)2CCH2CH3
OH

H3
CH3

Br

H2O

(CH3)2CCH2CH3
OEt

EtOH

(CH3)2CCH2CH3

C CH2

(CH3)3C-CH2-Br

CH3

(CH3)2C=CHCH3

,
, ,

.

CH3CH2CH2Br

AlBr3
(.)

CH3CHCH3
Br

, -,
, ,
, ,
.

(. 26.4.8).
, - ,
" ".
- [1,2]-
, (. 26.3.1..)
26.3.1.
( )
, "" .
,

2007

2008

SN2
X,
Y. Y
W-A-+ +A-B-W (. 26.8.1.)..

-
:
R

R -
-

A B
Y X

-
3- (VI) 13(18)- (VII).
VI -
, .
VI VII, [1,2]!
19

H
2

HO

1 10

3 4

11

12

Me

H MeMe

Me

18

13
14 H

Me

20

Me

15

21

Me

22

Me

17

Me

16

Me

XXVI

XXVII

[1,2]- ""
,
. - 2
3.
:

4 3, 5 4, 10 5,

9 10, 8 9, 14 8
13 14. 13 ,
18 13(18)-.

SN2-. ,

2008

2009

( 26.3).
26.3

H2O Me

Me

C1

Me

C7

Me

C12

14

13

18

C19

C6

C11

C15

Me

H2O
Me
H

C6

Me

C11

Me

C15

C12

H OH2

10

14

13

18

C7

Me

Me

10

H ... OH2

C1

C19

, .
, .. , (
VI VII )
, , ( ),
.

( > >
). .
,
.
-

(. . 13).
.
- , ,

R,

1,7- .

2009

2010

H
R

OH

OH

OH

-H

26.4.1..

, -,
,
. , ?
.

SN1

"" ) SN2 (

).

""

, , ,
, ..
, . , 3--3--1 2--3--2- ,
( 14C).
Me
Ph

14

C CH CH2

Ph

Me

14

14

C C Me + Me

C C

Me Me

Ph

Me Me

( )

( Ph)

, ,
, -
(. 26.5).

Me
+

Ph

C CH CH2
Me

Me

C CH Me

Me
XXVIII

2010

Me
Me

Ph
C CH Me

2011

(XXIX) :
Me
+

Ph

C CH CH2

Me

C CH Me

C CH Me

Me Me

Me Me

XXIX

-, VIII XXIX , , . ,
, ,
.
, 3----2, VIII,

Me
14

Ph

C CH

CH3
-TsOH

Me

14

C C

Ph

Me Me

Me OTs

TsO- o
SN2, VIII.

Me C
Me

H
C Me
OTs

S N2
-TsO-

XXVIII

TsO-,
-,
. ,

.

,
,

, .

2011

2012

, .
3,
25. , .

-,

- - ,
-

. e .

:

- > - > - > > -

,
( 26.5).

26.4.1.. .

- [2.2.1] (XXX),
(XXXI) - ,
(), () .
"" ( ).
1

CH3

CH3
CH3

O
OH

H
XXX

XXXII

XXXI

XXXIII

.
2- .
, (32+)
(h22+). ,
2012

2013

- ;
C1-C6.
1-C6 SN2.
7
4

5
6

[1,2]C

(26.8)

XXXIV

XXXIV

-, - 1-C6
X-,
SN1, .
, -.
7
1

[1,2]C

(26.9)

-X-

XXXVI

XXXV

IV V 2 , ,
, 7
.

6
4

2 1

3
1

7
1

(26.10)

()

-; , IV
V
:

2013

2014

XXXV + Y
Y

(26.11)

XXXIV + Y
Y
IV V , ,

(26.8) (26.9),
. ,

. .
. 1949 . , -,
-2- (-)
-.
-,

99,95%.

-, 92%,
8% ,
SN2.
6

AcOH

2
1

OBs

()

AcOH

()

OAc

AcOH
S N2

OAc

OBs
1

-2- (8%)
-2-

[1,2]- 1-C6, 2-
[1,2]- 3 2.

2014

2015

-; 3-- 2-, .. (. 26.3.1.).

[1,2]H

HH

H
H

(27.12)

1, 2, 3, 4 7.
5
6

3
1

[1,2]C

[1,2]H

[1,2]C

(27.13)

5
6

[1,2]H

[1,2]C

4
7

3
1

..

..

, 2-
14

, ,

.
. -2-,
14

2 8,

:
22%

7
7
6

OBs AcOH
2

OAc

15%
5

23%
4

40%

1, 2, 3, 4 7,
5 6. ,

2015

2016

, 1,3-
2 6 3 5 ( .
26.3.1.).

(27.14)

2
1

,
,
-,

.

(.,

1949),

, ..
,
, ,

1,

()

()

1-6

2:
6

6
4

4
7

-X-

3
1

,
,
. ,
, , .
, ,
(IV)

() ( 26.10)

, VI.
,
2016

2017

1 2 .
(26.11) :

+ Y

+
Y

()

( 26.10).
.
-2- SbF5

, , SO2-SO2ClF SO2ClF-SO2F2
- ,
, .. ,
.
7

SO2ClF-SO2F2

SbF5
5

SbF5
3

. , 11
.

( )
3,2- 6,2- 1,2-
,
(
26.13). -60
6:1:4.
, 3,2- ( 26.12) -60
"", 6,2- ( 26.14)
( 26.10) .

2017

2018

( 6:1:4
3, 5, 7, 4
1, 2, 6).

-156

" " 2,6 - ,

3, 5, 7, 4,
6 1,2.
, (1) ,

""

, -156 , (2)
"",
"",

-156
VI

6.

1s-

1970 . (.), , 1s 1, 2 6
1,5 .
1s- ,
, , 3,7
. ,
1, 2 6, ,
10-16 ,
(10-13 ), .
,
V, , " ".
,
,
. (26.8) (26.9):

2018

2019

-X-

-X-

X
(26.12):
H ()
H

H ()

H
H

H
(26.14):
H

H
H

" "

7-

(VII),

7-

(VIII)

. 2- (XXXIX)

.
X

H
CH3
XXXVII

XXXVIII

XXXIX

26.4.2.

1859 . . (XL), 1860 .

(XLI).

2019

2020

CH3 CH3
CH3

C CH3

H2SO4

CH3

OH OH

C C(CH3)3
O
XLI

XL

, .
,
1,2-.
.
, ,
(COOEt).
- , .
.
Ph2C
OH
MeCH
OH
MeCH
OH

CH2
OH

PhCOCPh3

CPh2

( Ph)

OH
CPh2

MeCOCHPh2

( )

OH
MeCOCH2Ph

CHPh
OH

CHMe

OHCH2CH3

OH

(
)

(-
)

[1,2]-
,
. "" ,

(. 26.3.1..).

2020

2021

R1

R2

R3

C R4

H+

R1

R2

R3

C R4

-H2O

OH OH2

OH OH

R3

C R4

[1,2]

OH

R2

R2
R1

R1

R2

C C R3

-H+

OH R4

R1

C C R3
O R4

(XL) (XLI)
(. . 3).

, , ..

. 218

18

,
.
,

. ,

- (.
; . 5,

5.4.3). -,

, ( )
:

R1

R2

R3

C R4

OH

R2

R2
R1

C C R3
OH R4

R1

C C R3 + H+
O R4

1--1-(-)-
(-) , ..
. ,
2021

2022

, :
Ph
CH2 C

Ph
CH C

Tol

Tol

OH

OH OH

OCHCH(Ph)Tol

, ,
.
, "
" , , (. 26.4.1),
, ,
:

R2
R2

R1

R2

C R2

R1

R2

C R2

R1

R1

OH
R2

OH OH
R2

R1

R2

C R2

C C R2
OH R2

R2

OH
, ,
,
. ,

2SO4

1,1--2,2---1,2-

- (LII),
2SO4 (LIII).
Me

C CPh2 H SO
2
4
O Me

Ph2C

CMe2

OH OH

XLII

HOAc

H2SO4

Ph

C CMe2
O

Ph

XLIII

, ,
( )
, ( )

2022

2023

, ( 2)
,

, ..
(. 26.4.1.).
, .
,
:
O

OH

Ph2C CHR

[1,2]H

Ph2C CH R

Ph2CHCR

(R = Ph)

OH

OH

[1,2]Ph

Ph2C CHR

PhCCH(R)Ph

(R = -)

OH

, :
OH O

O OH
-C3H7

-C3H7

C C CH3

C C CH3
CH3

CH3

OH O

O OH

H C C C6H5

H C C C6H5

C6H5

C6H5

=O.

R2 R3
R1

C C R4
OH NH2

HNO3
+

(H )

R2
R1

C C R3 + N2 + 2H2O
O R4

, -,
2023

2024

(. ).
: - > Ph > CH3.

-

,
. :

Ph
HO

Ph

C CH2 I Ag

- AgI

CH3

HO

C CH2

CH3

CH3

CH3

C CH2Ph

CH3
HgO

OH

C CH3

OH

: Ph >
> 3.
.

, ..
. , ,
, ,
,
. , , ,

, ..

:
R

R
C

2024

+ X

(26.15)

2025

(26.16)

- ,
-
" ", , , ,
(.

) , (.

-- (.

),

) .

, , .

, (., 1838),
,
, () 6565.
- -
.
Ar'
ArCOCOAr'

OH
-

Ar

C COO
OH

,
-.
-

h2()

[][-]. ,
- (. 8),
. ,
.
O
O

C C
Ph

Ph

OH

H
O O

H
O O
O

C C
Ph

Ph

C C
Ph

, :

2025

Ph

2026

Ar
Ph

C C

Ph

Ph + ArMgX

MgX

O O

Ph

C C

Ph

Ar

C C

Ph
O OMgX

O O

, =O (
; . 26.7.1).
:
R2
R1

C C

OR

R3

R1 R2
RO

O Cl

R1

C C R3

RO

O Cl

C C
O

R2

R3

, .

.
N

Cl
Ph

Me

Ph

OH

N Me
HOOC

Me

Ph

HCl
EtOH

Cl
H

EtOOC

O

,
.
,
.
R C H + CH2N2

-N2

R C CH3
O

O
R C R' + CH2N2

-N2

R C CH2R'
O

,
.

2026

2027

CH2 N N
R C R'

R C R'

CH2=N=N

CH2

R'

( )

-N2

CH2

CH2 R

R C R'

C R'

, ..
.
, , .

,
, , .
,
. BF3 AlCl3
.
, ..
, .

26.4..

. 24,
. 25. ,
.

3--1-.

2027

2028

NH2

N N
HNO2

CH2
H2O

OH

H2O

CH2OH

H2O

CH2NH2

HNO2

H2O

CH2

CH2 N N

,
.
3-8-,
,
.
-, -, - .
5- , ,
, .. .
- - ,
.

-. 4-8,
, :
CH2NH2

HNO2

OH
,
, :
OH

O
Br

C
R R'

i-PrMgBr

Br

-C3H8

R R'

2028

R
R'

2029

, R, R ,
R=R=H.

, (.

.
Hg

OAc

AcOH

CH2OAc + Hg

26.4.4.

,
, .. ,
. , ,
, .. .
.

,
- -
.
- .
R C Cl + CH2N2
O

-HCl

R C CHN2
O

Ag2O/H2O

PhCOOAg/Et3N

R CH2 COOH

, ,
.

.
, , .
. R
,

2029

2030

. -
R1CHN2 RCHR1COOH.

. ,

(
-),

( ),
,
, ,
, .
-N2

R C CH N N

C CHR

R C CH

(,

Ph2C=C=O)

, -:

C C

C C O

R N

R N C O

,
:
Me

Me
Me

C CHN2

Me

C CH

Me

Me

Me

Me

Me

C CH Me +
52%

Me
47%

1894 . --,
1,1--2-
.
Ar
C C
Ar'

H RO , NH2 , AlkLi, ArLi

Br

-HBr

2030

Ar

C C Ar'

2031

Br > I > Cl. ,

.
: ,

.
.
Ar

H
C C

Ar'

Ar
C C
Ar'

Br

Ar

C C Ar' + Br

Br

26.4.5.

( , ),
, -.
, ,
( ) ,
,
.
,
(26.15) (26.16):
R
R

B C

+ Nu

B C
Nu X

R
R

R
-X

B
Nu

B C
O

+ Nu

B C
Nu O

2031

-X

Nu O

2032

., 1970-1980-
, ,
, , .

26.4.5.a.

, (.
. 5), 100-125
,

2-6-1,3-

(LII),

.
R3B + CO

HOCH2CH2OH
100-125 oC

O
R3C

H2O2

CH2

O CH2

NaOH

R3C-OH

XLII

, R
, , ,
.
:
, -2-,
LIII LIV.
OH

B
OH

XLIV

XLIII

, ,
, ..
.
.
R

R
R3B + CO

R B C R

R B C O
R

R
B C R
R

R R

XLV

HOCH2CH2OH

R3C OH + HO

2032

B C R
O XLVI
B

O CH2
O

CH2

(26.17)

2033

.
, -,
,
[1,2]- .
R3B + CN

1. (F3CO)2O

R3B-C N 2. H2O2-NaOH

()

R3C-OH
( R)

. .

Et2BCH2CH3

Br2; CH2Cl2
h

Et

Et
Et

B CH CH3

Et

-HBr

OH

H2O: Br

Et

Et Et

Br2

B C CH3

-HBr

B CH CH3

(HO)2B C

Et

CH3

H2O: OH Br

Et

H2O2

Et

NaOH

C OH
CH3

26.4.5..

R3B ,
LV

26.17)

LVII

H2O

R3B + CO

OH -H2O2

R B C R
OH OH
XLVII

OH -H2O

R C R
O
R CH R
OH

NaOH, , NaOH
2O2, . ,
>
> ;
,

.
2033

2034

26.4.5.. ,

R3B BH4-
(r-)3 LV
( 26.17), ..
.
.
R3B + CO

XLV

LiBH4

R2B CH R

H2O/OH

RCH2OH

OH
H2O2
NaH2PO4-Na2HPO4

RCHO

.
R3B + PhO-CH-COO

PhO-CH

-PhO

R2B-R
H

R CH COO

RCH2COOH

BR2

26.4.5.

.
R3B + I2

CH3ONa
CH3OH

RI

, ,

2034

2035

Alk
H

BAlk2
C C
+ I2
R
R1

OH

B Alk

C C
R
I R1

R R1 I

H C C B Alk

-Alk2BI

Alk

C C
R

R1
Alk

. -,
lk , -, R R1
-, -.
, R1=H, -
R=lk. ,
Alk-H .
-
1-
1- (LVIII) .
MeO R
R B
H
-
C C
R2BH + BrC CR' (. . 7)
Br
R'

CH3ONa

XLVIII

R
R

C C

AcOH

R
R

R'

OMe

C C

H
R'

:
R2B
Br

C C

H
R'

NaOH

R B

C C

I2

R'

NaOH

C C

H
R'

OH

2035

2036

H
B

Br

+ BrC CR'

C C

R'

NaOH

OH
R'

CHR'

C H
HO

I2
NaOH

26.4.5. .

-
-

(,

, ..),
:
E
R

R3B

C Li

RC C

B R2

RC

R
C BR2

, ,
, .
RCH C
R''COOH
(E=H)

C C

BR'3

(MeO)2SO2
(E=CH3)

RC

RC

C BR'2
R'

H2O2
NaOH
[H ]

C BR'2

RC CR

2036

Me
R CH C

R'

O
R'2C

C C

R''

R O
CH3COOH

ClC C-BR3

RCH=CHR'

C BR'2

CO2 R'
RC

R''COOH

BR'2

Me R'

R''C(OR''')3
TiCl4
R''C(OR''')2
CO2

R'

R'CH=CRCOOH

2037

26.4.6.

-Me
.

()

CH3

CH3 CH CH2 Br

Br:

Br
CH CH2

OSO2Ar

CH3 CH CH2

CH3 CH CH2Br
OSO2CF3

OSO2Ar

CF3COOH

CH3 CH CH2 OSO2CF3

(3:1)

Br

:
:
Br
C C

.
,
. 26.7.

(LI) :
C

C
R

C
R

C
O

C
C

XLIX

-- -,
- .

2037

2038

R1
R1

R2

R3

C C

R2

(X = F, Cl, Br, OCOR)

O X

R3

, R (, ).

26.5.


,
. (R=lk):
R
O C

R C N X

N X

NH X

O
H
R

C N

R + X

R
O C

C N X

C NH R + X

O
;
(.
26.3.1.),

(, r =-).
: (1)
, (2-) R 9899% , (3) , ,

(4)

(, ,
, ).

-. , X,

2038

RCON:

2039

RCONH

, . ,

pea
(. 26.3.1.).
, ,
,
.

26.5.1.

(
) ( Na+r2),
, ,
. ,
, ..
.
-

RCONH2 + NaOBr

R-N=C=O

-O2

[R-NHCOOH]

RNH2

R . Na/r2
Na/r2, RNHCOOCH3,
( ). Na/r2

RNHCONHR

RCONHCONHR RN
RNH2 RCONH2 .
, :
O
C

COOH
NH + NaOBr

NH2
O

(-)

-- - .
R2C(OH)CONH2 + NaOBr R2C=O
,
2039

2040

OH

R C NH Br -H O
2
O

R C NH2 + Br2
O

R C N

C N R

Br

N-,
NH-,
-. , - [1,2] . ,
: r- ,

.

()

PhI(OCOCF3)2,

b(3)4

26.5.2.

.
RCON3

R-N=C=O

, , ,
, , .
:
,

(. . 18).

N2

.
, , ,
(. 26.4.4).

2040

2041

R C N N N

R C N

-N2

[1,2]

C N R

, ,
, , ,
:
R C N N N

C N R + N2

R3C-N3

R2C=NR + N2

,
, ,
e R3CN:. , .
a

.
R

NR

N3

N
+
80%

N3

20%

NHPh

PhNH2

26.5.3.

, O--
(RCONHOH) ,

2041

2042

R C NH-OCOR

R C N OCOR

C N R

-RCOO

(R=Alk, Ar)

, ..
.

26.5.4.

, ,
.
:
H+

RCOOH + HN3

R-N=C=O

H2O

RNH2

,
. ,
R=lk, . R=Ar,
, .
, .. .
NH- R;
.
+

R1

+ HN3

C NH

R1

.
:
O
+ HN3

NH

NH3 ,
(. 26.5.2).
,
:

2042

2043

R C OH

H
-H2O

R C + HN3

R C N N N

O
H

C N R

-N2

O
RNH2 + CO2

(. 26.4.2), (. 26.6).
+

R C R'

H N N N

R C R' + HN3

-H2O

R C R'

OH
N N N
R

C R'

-N2

R'

R'

C N

H2O

R'

C N

OH
C NH R
O

26.5.5.

PCl5
.
R C R'

PCl5

R'

C NH R
O

N OH

, ,
, PPh3, , SOCl2, . ,
, , .
RCONH2, .. ,

3 100 .

2043

2044

,
()- . e

H2O,

:
N OH
R C R'
R'

N OH2

()

C N

R'

R C R'

OH2

()

R'

-H

C N

C N

R
R'

H2O

C NH R
O

OH

, :
R
R'

C N
OH

R
R'

-H

NH

R'
R

OH

C N
OH

. ,
()- ,
, RR1C=N:+ .
, ,
: l4 PCl5, OSO3H
..
,
:
N OH

NH
O

26.5.6. N-

N--2-[2.2.2] (L)
, -.

2044

2045

AgNO3

Cl

Cl

(L)

-AgCl

MeOH

Ag

MeOH

N
OMe

,
:
Cl
HO NR

Ag

HO

HO NR

O
N

R
N

-H

-N- -N-

Ar3CNHX
Ar3CNHOH

PCl5

Ar2C=NAr
Ar2C=NAr

(
26.5.2).

26.6.

:
R

R
C O

C O

+ X

X
- , 2O RO-.
SN1

2045

2046

R-C-O

26.6.1.

(R= ,
)
.
R

R C O O H

R C O + ROH
R

,
. ,
: > > -r > Et >> Me.

LI, .
LII,
.
R

R C O OH

R C O OH2

R
R C O

-H2O

[1,2]

H2O

R LI

OH2
R C O
R

R C O + ROH
R

LII

26.6.2. -

( ) () RCOOH
(
) ,
:

2046

2047

R1 + Ph

R C

R C O

C O OH

R1

.

( 26.5.4):
O
+

R'

C R

R'

C R

R''CO3H

O O
R'

OH

O
R'

OH

O
+

-H

C R

C R

R C O

C R''

[1,2]
-R''COO

R'

OH

: (1) ,

18

, (),

,
18

, (2)

14

,
(..
RCOO-, .. ,
SN1- ).
-

F3 (

).
: > > > .
e

.
.
R-CHO

R'-COOOH

2047

R-COOH

2048

- ,
:
R C C R

R'-COOOH

R C O
O

O O

C R
O

.
C O

O
C O

R-COOOH

26.7. 1,2

, , ..

II.

: 1,2-
.
,
SN2
:
W:
A B
X

S N2

W
A B

Nu

Nu

A B

, , ,
, ..
:

2048

2049

R2C H
A B
X

R2C:

CR2
A B

A B

Nu

X
H A B

A B CR2
Nu

CR2
Nu

a
-, AW-B. (.
).

, , 1,2- (
26.4.6) 1,2- ( 26.4.6)
1,2- ( 26.3.1.).
,
. F
e .

26.7.1.

( = l,
r, I), -,
-,
.
H
R1

R3

C C C R4

R5O

R1 R3
R5O

C C C R4
O R2 H

R2 O X

Na ,
, , .
:
3
4

Cl

+ OR

5
6

2049

COOR

(26.18)

2050

[1,2]-
, ( 26.4.2),
:
R

R
R C C

R'O

+ OR'

R'O

C C

C C
O

O X

O X

(26.19)

(LIII) N

(LIV)

. ,
-
PhCH2

C CH2

OH

PhCH2CH2COOH

OH

PhCHCOCH3
Cl LIV

O Cl
LIII

OH

PhCH(CH3)COOH
( )

, .

. (26.18) 2-,
1 2

14

C, , 50%

25% .
1-6,
,
1-2, =O .
. ,
, , ..
2 6 2- .
,
(LV).

2050

2051

PhCH2 CO CH2Cl
PhCH CO CH3

OH

OH

PhCHCOCH2Cl
PhCH CO CH2

PhCH CH2
C

-Cl

Cl
*

-Cl

Cl
*

LV

* O

O + OH
H

*
COOH
*
+

* O
*

OH

Cl

OH

* O

LV

*
COOH

(1 : 1)

- , , ..
=O, -.

.
PhCH2 CO CH2Cl
PhCH CO CH3

OH

OH

PhCHCOCH2Cl
PhCH CO CH2
Cl

Cl
PhCH CH2 + OH
C

-Cl

PhCH CH2
C
O
LV

PhCH CH2
C
O OH

PhCH2CH2COO

-Cl

PhCH CH2COOH

Ph CH CH2
COOH

( )

2051

2052

H
R1

R3

R3

RO
R4
-ROH

C C C

R1 C
C R4
C
R2
Cl

R2 O Cl
R1
R2

O
R3

C C
R4
C

RO

R1
R2

O
R1
R2

R3

C C
R4
C
O OR
R1

ROH

R2

C C R3

O C

" SN2"

C CH R3

O C

R4

R4

OR

OR

-, R1R2
CR3R4.
- ,

( 26.19).
; 26.4.2.

26.7.2.

1,2-
, :
O

N:

N
Ph CH

Ph CH CH COPh
Br

H2O
NR2

Ph CH CH COPh
OH

2052

CH COPh

2053

- e,
-
,
RCH2

OEt

C R'

RCH C

R'

NH2 O

N OTs

( 26.5.5).
: - - .

(LVI), .
RCH2

C R'

R CH C R'

N OTs

N OTs

R CH C R' H2O
N
LVI

RCH C R'
NH2 O
R = OR, a
RCH(NH2)COOR.

26.7.3.

, , ,
. 15.
N,N-
. .
Ar2

C N
OAr1

Ar3

Ar2

CH3O(CH2CH2O)4CH3

PCl5 -:

2053

Ar3

C N
Ar1

2054

Ar2

Ar2CONHAr3 + PCl5

Ar3

C N

OAr1

Ar2

Cl

C N

Ar3

OAr1

1,3- o

.
O
Ar2

O
Ar2

C N

Ar2

C N

Ar1

C N
Ar1

Ar1

26.8.
26.8.1.

.
,
, ,
Z (Z = Ph, RCO ..), ,
:
R
Z CH2 N
R

NaNH2

R
Z CH N

R
R

Z CH NR2

R
(LVII)

(LVII),
.
. Z = r,
- (
),
:

2054

2055

CH3

CH3

CH3
CH

CH2NR2 NaNH2
CH3

CH

CH3

NR2

CH2

NR2

[2,3]

CH3

CH3
CH3

CH2

CH2NR2

CH2NR2

- ,
(. .10)
,
:
PhCOCH-S

CH3

PhCO-CH-SCH3

CH2Ph

CH2Ph

,

.
R
R N O

R N OR
R

, R -,
:
150-200 oC

C C
H
O

NR2

C C
H

NR2

, :
RCH2

O R'

PhLi ()
-PhH

R CH OR'
Li

2055

R
R'

CH O Li

2056

,
: > > > .
1,2- .
, [2,3] -
:
2

Ar2 CH
CH3

PhS CH
CH3 N
CH3
Ar

CH
O

R
Ph

Ar CH
CH3 1S

3
2
1

PhS CH
(CH3)2 N
(26.10)
Ar CH
O
R

(CH3O)3P

Ph

R
OH

26.8.2.

,
1,2-. ,

(. 26.1 26.2). ,
, : (1) -,

( N, N O) ,
, (2) -
,
.
:

2056

2057

a
b

2s+2a
( 4s+0)

2a+2s
( 4a+0s)

,
-
. , ,

C-N ( -) - (
-N ). ,
. .
(. 26.3).
, :

, .
,
.
, , N-

,
.
,
. ,
, N-
.
,

- ,
. ,

LVIII,
:

2057

2058

CH3

CH3

CH3

Ph CH N CH3

Ph CH N CH3

Ph CH N CH3

CH3

CH3

CH3

LVIII

(26.21)
CH3
Ph CH N CH3
CH3
26.3

() 1,2-

( )

1.

CH(Me)Ph

PhCOCH-NMe2CH(Me)Ph

97

CH(Me)Ph
NMe2CH(Me)Ph

2.

PhCOCD-NMe2CH2Ph

3.

90

PhCOCH-SMeCH2Ph

4.

CH2Ph

CH2Ph

PhCH-OC(Me)(Et)Ph

5.
6.

PhCH-OCH(Me)Et

7.

C(Me)(Et)Ph

80-90

CH(Me)Et

62

C(CH3)3

PhCH-OC(CH3)3

CH(Me)Et
8.

+
74

OCH(Me)Et

9.
10.

CHDPh

O-NMe2CHDPh

CH2Ph

O-NMe2CH2Ph

80

2058

2059

( ),
. ,
g-

(..

).
,
,
( 30 )
"" .
10
(26.21) ,
N--N-()-
, 30

,
,
( ).
,
.

. 26.3,

. , .

1,2-. -1-6- ,

( ).

2059

2060

Ph

Ph
Ph

20 oC

C O

C O

C O
Ph

Ph

Ph
k~10-5 c-1

Ph

Ph
C O

C O

Ph

C O

C O

Ph

Ph

5%

22%

48%

8%

Ph

74%

Ph

44%

Ph

C O
+

- (74%), - (22%)
- (5%),
- ,
, :
(48%) > (44%) > (8%). ,


: < < , ..

(,

. " "
(h2=O)

2060

2061

26.8.3.

-N -O, ?
, ..
,
, -60 . ,
, ,
.
ArCH O
R

ArCH O

ArCH=O
R:

,
, , SN2 (. 9,

).

, ,
LI, LVIII:
ArCH O

ArCH O:

(26.22)

(LIX)

. 9, SN2
,

:
Nu:

Nu

R + :Z

(26.23)

(.. Nu-R)

(26.22) (26.23) ,
" " Z ,
, , Z
(26.23), .

2061

2062

(26.22) ,
R , -.
, ( ), .
- ,
.

26.9. -
[3,3]- ,
26.3.2., [5,5]-
.

26.9.1. o

1,5- ,
. ,
3 ( 4) ,
.
CH3

300

Ph

165-185

CH3

Ph

,
,

.
,

PdCl2(PhCN)2

.
1,5- -
,

2062

2063

, :

C
C

,
.

,
, .
26.8.2.,

-3,4--1,5- (LX)
(99,7%) -,- 2,4-.
-, -, -, -.
H
H

Me
Me

Z
225 oC

Me
H Me
E

-, -

(LX) -

2063

(99,7%)

2064

H
H Me
H

Me
Z

Me
H
Me

-, -

Me

Me

H
Me
Me
E
H

-, -

LXI
, 87:13.
90%- , ..
.

.
8%, ,
6 /.
Me

Me

H
*
(87%)

Ph

Ph

*
Me

(S)

(R)-LXI

Ph

Me
Ph

Me

Me

*
(13%)

Me

Me *
H

(R)

(S)-LXI

,
,
- . , LXI - LXII,
.

2064

2065

N D

COOMe

N
D

1'

3'

2'

80 oC

1
4

COOMe

6
5

2'

3'

4
1

1'

2'

3'

COOMe

1'

Ph
N CH O

PhCHO

LXII

LXI

1,5- 3 , , ,
:
[3,3]

HO

HO

26.9.2.

-.
.
R
O

C
C

OH

O
200 oC

C-C=C-R

C-C=C-R

[3,3]- . , -.

-:

2065

2066

O
R

R*

R
*

OH

(R=Alk)

R
(*- 14)

*

: ,
,
, 14 (.
).
,
.
,
(, - 10-20

-).

300 .
;
.

( 1912
).
R

,
. , -,
- (LXIII) 97% -:

2066

2067

Me
O

H
OHC

Me

Me
OHC

H
Me

Me
H
H
Me

(>97%)

Me
H
Me
H

(<3%)

, (..
Ar-O-CH2-CH=CH-R),
, , :

OH

OCH2CH=CHCH2CH3

CH2CH3

OH

CH-CH=CHCH3

CH-CH=CH2

CH3

"
"

"
"

, ""
"" .
O

O H

CH3
CH

CH

CH2

CH
CH

CH2

CH2

CH3

CH3

"
"

O H
CH CH3
CH

CH

OH

CH

CH

CH
CH3

CH3

"
"

CH3

"",
.

2067

2068

-:
CH2R
A

CH2R

A C CH CH CH CH2

O B

CH3

CH3

H
A = H, R, OR ..
R = H, R, Ar, COR, COAr, COOR .

A C CH CH CH CHR
O B

,
-[1,5]- .
1

A
B

2C
3

O H
CH

CH

CH2

CH
CH

CH3

CH2R

CH2R

"" , CHCH2R
(. 1,3 - ; 26.3.1.).

,
.
in situ,
. , ,
- .
O
Me

O
Me
Me2CHCOOCHMe=CH2

NaH

Me

Me

2068

Me

Me

2069

NMe2

O
OH
Me

(MeO)2C(Me)NMe2

Me

140 oC

Me

NMe2
Me

Me

Me
H

OZnBr
Me

OZnBr
Me
Zn
Me2C(Br)COOCH2CH=CH2 80 oC
Me

Me

26.9.3. [3.3]-

1,5-
,
, [3,3]-. , ,
LXIII,
F .
C
D

B
E

C
D

B
E

A
F

LXIII

, ,
, (.,
,

LXI

LXII,

26.9.1).

1,5-
[3,3]-
.
, , ,
[3,3]-.