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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.
.
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
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
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 .
. 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.
.
-.
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
(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
.
,
(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
(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)
( , 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
, ,
. ,
- .
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
( )
. 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 .).
,
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
= 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, - ,
+ -,
(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 ( +)
,
( (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, ,
.
,
-
-. :
(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
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
(. . 2.8) ,
- .
.
.
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
2.5.3.
, (,
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+.
. ,
,
.
,
,
.
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
, " "
.
, , ,
. , " "
, .
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
()
()
- - "
"
,
- (IP=0,97 ) , - (IP=0,36 ).
, - , ,
, -,
202
203
5"
+'
+'
"4
'
'
(a)
5''
+'
+'
-'
-'
4''
. 2.34. - () - () -3,7
. " ".
. 2.34,, " " -
, + -. + -
4"(3")
5"(6")
"
"
+ - (. 2.34,), ,
-, + - . "
" .
1,2- -
203
204
- . , +
- -
+ -, .
, " " -
IP - ,
.
" " , , , .. -.
, , ,
1,2- .
, " "
.
-:
204
205
3.1................................................................................................................................... 206
3.2. .............................................................................. 209
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
,
, 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)
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.
2,9
-
6,2
2HF = H2F+ + F-
10,7 (0oC)
16,7
17,4
19,5
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
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..
() (+),
-
(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)3COH
O
3H2=
O
1,3,5-
(S=83,6 /.)
( -)
H
C
H3C
COOCH3
C C
C
COOCH3
H3C
- (S0 = 0.5 /.
,
.
, . :
Cl
Cl
[2.2.0]
, ,
, S .
H3
CH3
(S=0.4 /.)
-1,2-
CH3
-1,2-
,
1-5 ,
, .
235
236
2
2
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
. 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
()
, .
(, ,
) ,
,
(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
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
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]
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
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)
R...H...B,
c
R
-G# Go.
:
+
1/Ka(BH )
B + SH ()
R() + B
kb
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-, -
.
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-.
282
283
. 3.13.
. 3.14.
25
Z==0,
const=lgKa[ZC6H4(CH2)nCOOH],
..
lg
( )
= Z
( )
(3.29)
(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
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
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.
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 +]#
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
( )
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) -:
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
,
(+)-, ..
( ) :
( )
- , ,
, .
,
,
-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
CH3 C CH2 C
2-
CH3
CH3
CH3
2,2,4,4-
CH3
CH3
3-
CH3
CH3
4
CH3
4
CH3 CH3
CH3
2,3,5--4-
CH3
2
CH2
2--4-
CH2 CH3
3
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
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
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
:
CH3CH2CH3 + Br.
CH3CH2CH3 + Br.
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 /)
.
:
> > .
,
, -:
.
.
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
R-SO3H. ,
RSO2Cl
RSO2Cl + 2 NaOH
-
.
, 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
, 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
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
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)2CH + SbF5- + HC(CH3)3
SO2ClF
- 78
,
, (,
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
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
N (CH3)3 I
5.
(. 4):
378
379
Pt ; t
C C
H H
C + H2
:
CH3CH2CH2CH3
Pt; 500
: , ,
-, (. . 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
CCl4
(95%)
0(-5)0C
Br
-1,2-
CH3CH=CHCH3 + Cl2
CH3CH2CH=CH2 + Cl2
CCl4
-100C
CCl4
00C
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
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
O
C6H5CH=CHCH3 +
NBr
- H2O
N-
( ) 5:
O
NH + Br2
NaOH
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 )
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
.
,
.
:
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
.
.
([2.2.1]--2):
D
D
+ DCl
(57%)
+
Cl
Cl
D
+
Cl
(41%)
(2%)
DCl -;
. -
.
404
405
- ,
,
.
,
,
.
. (. . 11).
5.4.3.. .
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
, :
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
:
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
CH3(CH2)3CH=CH2
C6H5 C=CH2
CH3
2) NaBH4; H2O
OH
C6H5 C-CH3
CH3
(100%)
(CH3)3C-CH=CH2
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
(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
421
422
- C4H9CH=CH2 + (C2H5)2N-Cl + SO3
CH2Cl2
-C4H9 CHCH2Cl
(88%)
OSO2N(C2H5)2
Cl
N-Cl + SO3
CH2Cl2
+ 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
. . 1933 .
422
423
,
.
, ,
O
C
O
C
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
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
425
426
5.4.5.. N .
1942 . .
, N-
CCl4, ,
(
- ). N-
(NBS) ( )
:
O
O
NaOH
NH + Br2
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
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
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
+ 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
2) H C
3
CH=CH2
CH3CH2
2) Na2SO3 - HOH
CH3
3)
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%)
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
CH3
2) Zn - CH3COOH - H2O
H(O)C(CH2)7COOCH3
O + O=C(CH3)2
(84%)
,
.
,
:
CH3CH2CH2
H
C
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
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
(, ,
444
445
:
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
. ,
-,
-:
BH3 B B
, BH3
:
2BH3 = B2H6 ,
.
BH3
B H. ,
BH3 B2H6 -,
446
447
CH3, ,
- B H :
..
B
H
+
H
..
BHB ,
.
( ),
, .
: B5H9, B6H10 ,
,
, ,
.
( ).
-
:
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
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
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
,
,
(. 4):
.
,
,
, , 10-8 /.
.
.
. , ,
,
; -
() ,
458
459
:
.
C6H5
C6H5
C6H5
...-CH2
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
:
Cl3CLi + C4H10
-700C
, RLi,
1,1- :
. -1200
CH2Cl2
+ C4H9Li
-BuLi,
C6H5CHBr2
,-
()
- 780
- 780
-800
.. CHCl + LiCl
..
-C4H9Li,
C6H5CH2Br
LiCHCl2 + C4H10
..
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
- 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
Cl
N+(CH3)(C8H17)3Cl-
Cl
CH3(CH2)3CH=CH2
(85%)
C6H5 CH CH2
C
Cl
Cl
(70%)
CH3(CH2)3 CH CH2
N+(CH3)(C8H17)3Cl-
Cl
H
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
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
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
(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
.
, - (. 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
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
6CH2
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
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
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
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
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-
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%)
-.
-
. 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
, :
= 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
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%)
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
-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.
=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
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
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
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
CH2
CH CHCl
H2O; 100 C
CH2
CH2Cl
CH C
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
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
80 :
80%
20%
0 :
70%
30%
+40 :
20%
80%
1,4- .
1,3:
CH2
CH CH CH2 + Br2
CH2
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
(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
(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
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
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
:
O C O
C
250 - 280
+ CO2
,
, , , 2.
-
, ,
.
- (. . 6)
,
35%, :
CH3CH2CH2C
CH
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
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
(. . 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
CHCH2CH3
(18%)
,
, .
, .
, KMnO4
:
R'2C
C CR''2
KMnO4
H2O
R'2C C CR''2
OH OH
.
2,
:
R'CH C CHR''
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
(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
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
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
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
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
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
; 36
-C4H9
CH2
-C4H9
(2%)
(CH3)2C
H3C
H3C
; 36
(98%)
(100%)
.
, :
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
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-
590
591
8
8.1. ................................................................................................................................. 591
8.2. ........................................................ 593
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
Td
(, )
Oh
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).
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
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)
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
(. , 1904).
.
1904 . ,
(-)- (XLV).
CH3
C6H5 C C
O
O
O
1. CH3MgI
+
2. H3O
C 6 H5
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
H
Al
OH
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
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
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)
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
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
9.3.1.
................................................................................................................................ 726
9.3.2. ................................... 736
9.4. ...................... 737
.
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.
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.
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. -
:S
XNH2
NH2
NH2
C S R + (CH3)2S
NH2
S-
+ RS(CH3)2X
683
684
4.
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- ,
.
685
686
H
+
Nu
Nu
H
C
R1 R2
R2
SN2
R1
H
Nu
C
R1
R2
. 9.1.
.
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:- .
:
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
(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
-,
- (. 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
+ CH3I
k2
25oC
CH3Cl + I
709
(9.2)
710
N3
+ -C4H9Br
k2
25oC
-C4H9N3 + Br
(9.3)
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 (.) + (.)
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
714
715
. Nu-
, -, ,
, -,
( 45 ) R4N+
Nu- , ..
.
SN2-
NaCN -,
- (
).
SN2-,
:
+
6H5CH2N (C2H5)3Cl
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
+
(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
,-
,
, , ,
,
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
(. 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*
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
- ,
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
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+,
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
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
CH3 CH CH2CH3
OH
FSO3H - SbF5
FSO3H - SbF5
SO2 (.)
-110 oC
(CH3)3C
(CH3)3C + H3O
CH3 CH CH2CH3
OH2
+ H3O
FSO3H - SbF5
FSO3H - SbF5
SO2 (.)
-30 oC
FSO3H - SbF5
(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- :
+
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
10.1.
()
,
.
,
-. -
, :
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
C2H5OH; 40 oC
(64%)
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
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
(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-,
,
- ,
. ,
- , -,
- ,
,
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-, .
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
(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
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
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
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
(20%)
R1CH2CHXR2 - -:
R1
R2
R1
B:
R1CH2CHR2
+
H
+ BH + X:
2
R
:
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,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
816
(13%) OC
2H5
817
CH3CHCH3 (H3)3CO K
(H3)3COH
Br
CH3CH CH2
(98%)
,
:
CH3
CH3CH2CCH3
Br
(2H5)3CO K
(2H5)3COH
(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
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
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
828
829
11.1.
,
.
, ,
.. ,
,
.
. 11.1.
H
H C
H
, 1,10
, 109
, 0,96
, 110
, 1,43
, 109
.11.1.
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)3CHCH3
(96%)
OH
OH
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%)
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
(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.. .
,
.
.
,
.
,
.
844
845
.
r HI
.
7590%:
CH 3CH 2CH 2CH 2OH
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 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
OH
Br
KI + 85%H 3PO 4
80 o C
(60%)
.
- :
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
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
H Br
OH
(86%)
Br
(14%)
(20%)
Br
1,2-
Br
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
RCH 2 O
PBr 2 + Br
H
Br
+ RCH 2 O
PBr 2
H
2
,
r3 I3
:
(CH 3)2CHCH 2OH + PBr 3
, 0
, 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
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%)
(15%)
Br
(26%)
(11%)
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
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
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
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
Ph3PCCl3 Cl
CCl3
855
856
:
+
Ph3P Cl CCl3
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
Cl
CH3CN
20 oC
Cl
(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
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%)
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
,
, .
,
:
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
863
864
, 2,
, - -:
RCH2CH2OH + H2SO4
HSO4
RCH2CH2OH2 HSO4
E2
+ RCH2CH2OH2
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
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
C5H 5N . CrO 3. H Cl
CH 2Cl2; 25 oC
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
CCH 2OH
CH 3(CH 2)4C
C-CHO (84%)
7)
(CH 2)6-CH 2OH
C5H 5N . CrO 3. H Cl
CH 2Cl2; 25 oC 2
(CH 2)6-CHO
(80%)
14--8 Z - -
8)
H
CH 3(CH 2)3
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
,
:
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
OH
CrO 3-H 2O-H 2SO 4
(95%)
; 20 oC
OH
O (90%)
(CH 3)3C
CH 3CH CH CH C CH
(88%)
CH 3CH CH CH C CH
O
OH
C 6H 5CH C CH
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
(2) R2C-O-Cr
B:
OH
IV
C O + BH + HO-Cr
R
O
O
, , (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
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
,
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
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-
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
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
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
, (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
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
:.
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
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
H 5IO6
-
OH
Pb(OCOCH 3)4
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
- -,
-
-. , ,
. 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
, 2. --
112 33,
sp3- .
( .),
,
.
11.3.2.
:
,
..
11.3.2..
.
:
BrCH 2CH 2OH
H 2SO4
130 o C
.
, ,
, - :
897
898
(CH 3)3C
KHSO 4
100 o C
(CH 2)3CH 3 + H 2O
.
, .
.
11.3.2..
(. 5, . 1), ,
,
. ,
, :
1) Hg(OAc) 2;
(92%)
.
:
CH3
1) (F3COO)2Hg; (CH3)3COH
2) NaBH4
O CH CH3
(98%)
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
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
[2,2,2]
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
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%)
(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,
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)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
.
.
: 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
12.11.1.
....................................................................................................................... 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
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-, .
- == ,
4
5
6
N
..
N1
4
3
O
1
4
3
3
+
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
CH2(CH2) nCH3
20o C
.
,
.
.
.
:
ArBr + 2Na
ArNa + Na Br
ArCH 2R + Na Br
e ,
,
.
-
- 1- :
C 6H 5Br + CH 3(CH 2)2CH 2Br + 2Na
20 o C
, -
-.
,
980
981
-
:
R 1M + R 2X
R 1R 2 + MX
+ 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
CHCH 2CH 3 +
Cl
CH 2CHCH 3 +
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
- ,
-.
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.
, .
-
.
.
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
2) H3O ; H2O
(90-95%)
2 5:
999
1000
CH3
CH3
Na; NH3;
(50%)
C2H5OH, - 33 oC
1-1,4:
OCH 3
OCH 3
(84%)
2-
, ,-:
O
OCH3
O
H3O
5% H2SO4; 20 oC
to
H2O
,
.
, :
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-
OH
Na; NH3;
C2H5OH
0-20 o
:
1001
1002
Li
(80%)
9,10-,
1,4,5,8,9,10-.
1002
1003
13
13.1. 1005
13.2.
............................................................................................................................ 1008
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
,
, .
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
-
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
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
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]
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+;
+
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
- .
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
-9,1
-8,2
-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
+
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
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
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-
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
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%)
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-
()
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
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 )
(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% - (-
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
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
n-CH3O-C6H4CO-C6H4-n
(84%)
.
,
I ,
-:
X
+ AlkC
AlCl3
Cl
1092
O
Alk
1093
-/- 0,03
0,01-0,03. -
0,5%.
-. -
,
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
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
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
, , ,
+
CH3 .. + CH3
CH3 + CH3
, ,
. NaCl
. ,
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
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
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'
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
(II)
HCl
:
..
+
2 R2NH2Cl + 3 SnCl4 + H2O
.
, --,
(. . 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
,
.
.
, , , , , ,
.
,
(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
,
.
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-)
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
,
.
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.
-),
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
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:
...
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
,
,
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
:
(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.
: - -:
.
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
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 ( 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
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
; 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
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
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
-.
, (. ):
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
+ 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
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
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
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
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
H2O
ArCH-NH2
H +
CH2=NH2
ArCH=NH + CH3NH2
H2O
+
- 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
Cl
[ArCH=NHC6H5]2SnCl62-
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;
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%)
,
:
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
[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
,
,
(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
-; -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
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
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
H2O
(90%)
(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
C6H5CH=CH CH2CH3
O
(28%)
1) CH3CH2MgBr
+
2) H3O
CH2CH3
C6H5CH=CH C CH2CH3 +
(30%)
OH
(70%)
1) CH3CH2MgBr
+
2) H3O
(100%)
C6H5CH=CH C6H5
O
1) CH3CH2MgBr
+
2) H3O
C2H5
C6H5CH=CH C C6H5 +
(1%)
OH
(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
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
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
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
-
KOH
-
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
17.1. -
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,
),
oe, ,
(RO)2l, RSO2Cl, .
.
O
1) ; ; -78
2) (H3)3SiCl
OSi(CH3)3
99%
16
(.) -
1336
1337
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
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
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
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
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
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
-, .
, .
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
.
,
- ,
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
1) C2H5ONa
2) H2O-H2SO4
1) C2H5ONa
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%
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
,- , ,
(. 17.5).
17.5
, - , .
CH3(CH2)5C
O
H
+ CH2(COOH)2
; 100 oC
; 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
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
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
OB(C4H9)2
1384
1385
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%
,
.
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
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
,-
,- .
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
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
CH3(CH2)15CH2COOH
HgO; Br2
O
CCl4; 80
CCl4
80 O
- .
. 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
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
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%
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
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)
18.5.
- : PCl3, PBr3,
PCl5, SOCl2 .
, - l
SOCl2 .
RCOOH + SOCl2
N(C2H5)3
+ HCl + SO2
RC
Cl
CH3CH2CH2CH2COOH + SOCl2
CH3
COOH + SOCl2
H 3C
C 5H 5N
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
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
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
OCH 2CH 3
RCH
; 00
NHCBz
OC
OCH2CH3
NHCBz
O
C
RCH
O
+ NH 2CH
OC
OCH2CH3
NHCBz
COOCH3
00
R1
O
RCH
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
HCl
CH 3CH2OH
CH3(CH 2)7COOCH3
96%
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
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
,
.
18.8.1.. -
SN2 -
-
.
-
(, ), -
. (. .9)
,
,
, .
18--6-.
1454
1455
CH3CH2COONa + . CH3(CH2)3Cl
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
()
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
ArCOOCH3 + 3 H2SO4
:
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
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
19.6.
............................................................................... 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)
(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 +
( )
( )
( )
10
R-m + Z-CN R- CN
( )
11
R-m + Z-Rn R- Rn
( )
( )
R-C-C-OH
13
R-m + O 2
H 3O
ROOH
( )
[H]
()
R-O
14
R-m + Z2 R-Z
()
15
R-m + S8 R-S-
( )
( )
17
( )
18
( )
19
( )
20
( ,
)
21
()
22
R-m + CO R2CO
()
1475
1476
23
( )
-
, ..
.
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
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
1480
NO2
-100 oC
+ C6H5Li
Br
NO2
C6H5Br +
(97%)
Li
C6Cl6 + -C4H9Li
(C6H5)2C=CHBr + -C4H9Li
-75 oC
-76 oC
-C4H9Cl + C6Cl5Li
(82%)
COOLi
COOH
-75 oC
+ 2-C4H9Li
(62%)
-C4H9I +
Li
I
CCl4 + -C4H9Li
-100 oC
, - 78
-100. ,
, , ,
, :
(CH3)3SiO
Br
+ AlkLi
(CH3)3SiO
Li
CH2CH2Br
+ AlkLi
CH2CH2Br
Br
Li
+ AlkBr
+ AlkBr
O
+ AlkBr
+ AlkLi
Br
Li
, .
.
( 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
(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-
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)2Cu]Li + 6H5I
[(C4H9)2Cu]Li +
(90%)
(91%)
-C7H15
-C7H15
-1--1
[(CH3)2Cu]Li +
-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
Li
CH3
Cu
Li
CHCH=CCH3
O
,
, . ,
, [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
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
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'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
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
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
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 ( -) .
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
[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
- .
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
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
: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%)
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
:
(CH3)3Tl + 2LiBr
( ) TlI 3I,
:
CH3I + TlI
CH3TlI2
CH3Li
(CH3)3Tl
(.21).
()
) ()
, , , ..
Ar-m + TlX3
ArTlX2
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
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
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
R4Sn ,
, .
:
/
Bu4Sn + 4MgCl
3Bu4Sn + 4[AlCl3.NR3]
, ,
, (>=, -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-...
nBu3SnH + (CH3)3SiO-(Si-O)nSi(CH3)3
CH3
CH3
n/2 Bu2SnO +
n/2 Bu2SnH2
,
.
.
:
R3SnH + R'X
R3SnX + R'H
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
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
20.5. -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
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)
-,
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
()
()
1559
1560
( )
, ,
, .
. ,
, , 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
Ph3P
CH3 + PhLi
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 =
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 -
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''
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
(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)
, . 20.1. . , RSiMe3 -
, R2Hg (R = 2, CF2COOMe ,
CFCICOQMe, PhCC, 6H6, CF3) -2-Bu4N+I-
, . 20.1.. ,
R2Hg
HCl
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
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 -
- - 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
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
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
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%
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,
:
-,
.
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-:
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
()
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
()
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
21.7. 1644
21.7.1. ............................................................................................................ 1644
21.7.2 . ..................................................................................................................... 1645
21.7.3. ............................................................................................................... 1646
21.7.4. ............................................................................................................ 1647
21.7.5. .............................................................................................................. 1648
,
,
,
.
, ,
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-
,
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
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- ,
.
.
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
CH3NH2 + H3O+
25
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
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
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
R3NH Cl + R3N-N=O
Cl
N- 0 ,
N
, .
N-
R2NH + HCl + NaNO 2
0-5 oC
H2O
N-
0-5 oC
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
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
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%
,
,
- -,
,
, 4:1.
-,
( 24).
, ,
, ..
, :
1641
1642
120-140 oC
H2O
(CH3CH2CH3)2N(CH2CH2CH2CH3)2OH
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
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
22.1.
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%
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%
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) :
ArNO2
ArNO
ArNH-OH
ArNH2
ArNO2
ArNO
O
ArN=N-Ar
ArNH-OH
ArN=NAr
ArNH-NHAr
,
.
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%
- -
. ,
, .
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
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
( ),
. -
-
, .
N- O- (/)
. 75%-85%,
15%-18% 5% . ,
,
. , ,
, -
.
RCH2Br + AgNO2
ArCH2Br + AgNO2
0-20 o C
0-10 o C
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
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
. -
.
.
.
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
R2CCH2NR2 + H2O
NO2
.
5.
-
.
, .
O
2 RCH
+ 2H+
O
O
2 R2C
+ 2H+
H2O
0-5 o C
H2O
0-5 o C
. 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 .
.
.
.
. ,
,
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
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
ArNH2 + H3O
ArNH3 + H2O
1674
1675
.
N-,
. 1900 .
Ar-N-N=O + X
H H
, ,
.
ArNH-N=O + H3O
ArNH-N=OH + H2O
ArN=N-OH + H3O
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 ;
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%
0 oC
CH3COOC2H5
77 o C
20 o C
3C6H5N2Cl.BiCl3 + 2Bi
46%
5-15 oC
(C6H5)2SbCl + N 2 + 2ZnCl2
, , ,
,
.
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
CH Cl ; -70 oC
, .
() . 1886
.
C6H5I + Cl2
CHCl3
0 oC
C6H5ICl2
87-94%
().
1687
1688
C6H5ICl2 + 2NaOH
H2O
20 o C
54%
100
().
2C6H5I=O
100 o C
H2O
O
C6H5I + C6H5I
92-95%
,
(()).
30 oC
C6H5I(O-C
98%
)2
CH3
O
C6H5I(O-C
)2
CF3
(III) - -,
,
- (III)
().
C6H5I(OCOCH3)2 + 2NaOH
C6H5I(OCOCH3)2 + CH3
H2O
20 oC
Cl(CH2)2Cl
SO3H
C6H5I
88%
OH
OTs
+ 2CH3COOH
,
-
.
+ 2C6H5I
OH
OTs
CH2Cl2
+ 2C6H5I + H2O
OTs
OTs
ArNH2 + 2C6H5I(OCOCH3)2
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
H2SO4
Ar IOSO3H + Ar H 0-5 oC
1
Ar IAr HSO4
NaBF4
100 oC
-
80 oC
-
60 oC
-
97-98%
98%
98%
98%
70-80%
20 oC
-
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
OK
7.
80 oC
+ (C6H5)2I Cl
(CH3)3COH
CH3
O
CH3
+ KCl + C6H5I
C6H5
68%
9.
200 oC
(C6H5)2Br BF4 + N
C6H5N(C2H5)2
88%
C6H5
BF4 + C6H5Br
N
85%
,
.
, ,
.
-
-.
70 oC
C2H5OH
70 oC
C2H5OH
100%
1690
68%
92%
1691
90 oC
(CH3)2CHOH
C6H5OCH(CH3)2 + C6H6 +
92%
4%
4%
90 oC
C6H5OCH(CH3)2 + C6H6 +
(CH3)2CHOH
69%
31%
31%
-,,
, ,
, , :
(C6H5)2I . + (CH3)2CH-O .
1) (C6H5)2I + (CH3)2CH-O
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
, .
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.
0-5 o C
H2O
1693
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).
, ,
.
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
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
, ,
- .
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%
- ,
, -(-) .
:
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 )
.
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
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).
-:
H2O
0-5 oC
. 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
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
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
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;
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 + 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
ArN N HSO 4
H2 O;100 C
ArOH + N 2 + H2SO4
H2 SO4 ;H2 O
, SN1,
.
15.
.
:
N N HSO4
+ H2O
OH
+ N2 + H2SO4
NO2
NO2
81-86%
N N HSO4
OCH3
OH
OCH3
+ N2 + H2SO4
8O-90%
N N HSO4
OH
+ 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
+ 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
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
. 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
CH3COOH + C2H5OH
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
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
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
CH3
CH3
H2O -
O
96%
:
0-5 oC
H2O
0-20 oC
H2O
2(NaO3S)2NO + 4KCl
(NaO3S)2N-OH + CH3COONa
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
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
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.
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.
24.3.
............................................................................................................................ 1801
24.4. -................................................................................... 1806
24.5. - 1808
24.6. . 1812
24.6.1. ...................................................................................... 1815
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
)
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
.24.4
13
-100. G,
-.
G
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
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
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
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
- -1,4.
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
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
1835
80%
1836
CH2
(CH3)3COK
45%
Cl
CH3
CH2N2; Pd(OAc)2
H2
75%
85%
CH3
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
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) , ..
()
(s)
1859
1860
(a)
...
...
s-
...
(s)
...
(a)
(s)
(a)
(s)
(a)
(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) -
.
(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
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)-
(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
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 =
(25.5)
G1 = ( ) - ( )
E2 =
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
, - (. . 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'
" "
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
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 ).
1919
1920
lnk
(=-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
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
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 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
: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
: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
, , ,
.
.
.
, ,
..
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%
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
.
, -, 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
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
26.8. 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)
,
. , ,
,
-,
:
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)
(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
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
CH2 CH2CH2
H
14
CH2CH2 CH2
HNO2
1,314
, 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
XIV
C CH2CH2CH3
XV
26.3.1..
II
XI.
(,
).
(,
..), .
, .
, W ,
-, Y- (
, ),
1990
1991
(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)
[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
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
, , ,
.
()+
. 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]-
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
(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 .
:
26.4.1.. .
- [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
[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
""
, -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.
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'
-HBr
2030
Ar
C C Ar'
2031
.
.
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
(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
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]-.