Вы находитесь на странице: 1из 240

NMR Spectroscopy

An Introduction
H. Gunther
Professor of Organic Chemistry
University of Sjegen
Federal Republic of Germany
Translation: Robert W. Gleason,
Professor of Chemistry
Chairman, Division of the Natural Sciences,
Middlebury College, Vermont, U.S.A.

JOHN WILEY & SONS


CHICHESTER NEW YORK BRISBANE TORONTO

X.


- . . .
- . H. M.

1984

24.5
99
541.15 + 539.194

99

X.
: . . M.;
, 1984. 478 ., .
. .
- .
, , .

24.5
541

1805000000285
10984, . 1
041(01)-84

M I. I.

1980 by John Wiley & Sons, Ltd.


, , 1984

(),
1945 . . . , , ,

, , .
1953 ., ,
, ,
, ,
.
, .
, ,
,
.
,
, .

.

, .

. X. ()
1973 . *
.
1980 . .
Gunther H. NMR-Spectroskopie, Georg Thieme Verlag, Stuttgart, 1973.

. X.
. , .
,
.
. . , , , . IIV. , - ,
( ) . , ,
. V, VI, VIII X,

.

, , . ,
13C
19F. , , , (. VII, IX)
,
. , -,

.
- -, , , .

,
,
, , .
, 1980 .,
,
.
, .
. X. . 4 5 . IX -

*.
( ) .

,
. , , - , , -
, . -
,
. , ,
(19781982).
. . H. . , .
,
, , ,
.
I, II, IV, VIII, X, . 12 XI . . , H. M. .
H.
.
* Gunther H. NMR-Spectroskopie, Georg Thieme Verlag, Stuttgart 2 verbesserte Auflage, 1983.

(1973.)

, - (). ,
,
.
, .
-
, .
,
- . VII, . IX
. ,
,
. X. , . IX

-. , , 15N,
29
Si ,
. ,
.
, . ,
.
, ,
.
1973 ., - ,
.


. - .
- . .
P. . (-) . VII . .
(), , . , -
.
.
, 1979 .


,
, .

.
, , . -
. . ,
. , - -
H. M. . .
.
.
X.
, 1983 .

11

'

Ii0

,
, . 1945 . , ,
, ,


() . , 50- ,
.


.
.
S0
,

Ei . ,
. . .
, , (. 1).
, . 1 H,
19
F, 14N 15N, , .
12
C, ,

. 1.
B0;
.

.
13C, 1,1 %. . 2
. 1,4 T 60.
,
, , .

HC-O-CH2-CH3

-CH,

2. .

12

16O0C

. 3.
.

.
. -,
. .
. -,

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

() , - , , .

13

, . ,
,
, , . - , , - J,
, . , ,
, .

,
. . 4O0C
, 16O0C
(. 3). (87,8 /),
,
.
H3C
N-C

N=C4'
H3C
H


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

C6H6

12

18

,
. ,
. 19
13
15
31
F, C, N P.
.
,
. , . .
- ,
,
-.
, .
,
, , .

. 4.
.
, .
,
.

. , CeH5
C6H5
- 266+22
,
, . . 4 t
. , ,
, . .
() .
^ ,
-


(), , , ,
- . . - (, , ), ,
, .
, .
1. , . H, *. (T);
4
10 ,
().

* H
,
. , .

16

2.
(), .
/,
/(-), 4,184 , / /(-) .
3. .
2 4,
.
4. 0
. 4-10~ 7 ~2 "2.

I


I


,

. I l V l . : . V I I .

1.

.
, , , P, .

U = Y/1
(!-
. , .
. . ,
, z
H (= //2)

(1.2)
, ,
, , .

/==/, 1-1, 1-2

V i . ;
(1.3)
/ .
, , 2/-f- '

. I

18

.*

. I. 1.

. I. 2.
.

mx=-1/2.

;
-

( / = 1/2) -

1 = 1/2, - , *, (1.2)
(1.4)
P _ /
, , mi = 1/2 / = 1/2.
-
\hl = yh/2
(1.5)
, , 2- (

z .
(. 1.1, ). , , (1.5)

(L6)

^N g-, , a JAN .
, = //4

(1.7)

, h ,
. UN 5,0505- 10~27 /. (1.5) (1.6) , \ = N |AN.
* , , .

19

- -1/2

S0 = O

B0 >0

, .
,
/ = 1/2 / = 1/2.
. V. , . .
^O 1/2 , . . . S0 MO^ JA S0. S0 z,
V . I. 1,6, O^
Af = 2JA2S0

(1.8)

So Ji2S0
JA2S0 (. 1.2).
, , S0.
-,
. , , = hv,
L9

Av 0 = 2JA2S0 = Y^S0

v0 = (Y/2n)S0

Co0 = YS 0 (TaK = 2nv)

< )
(I. 10)

(I. 10) ,
.
, . 1.2,

V 0 ( ) (I. 10)
S0, )
(/

' I- I.

20

MP. I

21

. YH = 2,675 -10 T~ -C-'


1,4 T VQ = 60 , K =
= 5 , . . .
2.

(1.10)
, ,
, . .

, J = 1/2.
, , (. 1.3).
.
,
, . . . - (. 1.3,6).
, .
, ,
, . -

. 1.3.


; . .

. I. 4. .

, ,
,
.
,
, . .
.
,
, ,
. ., ,
. 1.4. , ,
.
, .
, .
, .
,
. 5
, , M.

, , ,
M.
(1.10).

22

. I

23

,

. M.

3.


, , , .
. ,

, ,

= exp(-\hBo!2nkT)~\-

(1.11)

JVg JV 0
, ,
k , T . ,
(JVp ;>, J V a ) .
1,4 T
0,021 /.
, , , , 0,001 %.
5 (. 1.5).
, , ,
.
, ,
. , ,
. , . , ,

. I. 5. - .

: ,
. . , , L, ,
.
,
. ,
. .

S0 , , , 0,


= (3/2) (3 cos2 9 - 1) "3

(1.12)

^0 . S0 .
3 c o s 2 0 1
. ,
3 c o s z 0 1 XJE, , (3 COS2O,,., , 0/3. , .

1 .

24

100 10 (
I

. J

1 1 IMKM

3-10

3-

3-10

3-12

_ I_
_ I_
_ _ _ _I_

- /
uifjubnuiiux

- 14

/
-

. I. 6. .

. , , . , ,
. IX , .
, (I. 12) , 0 = 54,7. ,
54,7,
,
, ,
0 =
= 54,7.

, . ,
(1.11), , .
.

, , .
. VII.
, -
,
.

1,4 2,3 T. , , . ,

25


(. I. 6).
(I. 10) : ( ) , , ( ).
.
, .
, ,
B0 AS.

. , , , ,
.

.
. ,
. , .
( 10 T),
. (1.11) .
.
,
, .
4.

, . , ,
, 1/2.
(1.2) mi = I, I1,
/ 2, . . . , /. , , . 1.7. , , (7 = 0),

26

27

. I

I
1

H3C4

,
N-C

H3C

"

19 F

. 1.7.
/ = 1 .
-S 0 =O

B0Xl
'7O '5N

I^ 1/2. - ,
/, - - . , -,
, ,
. 1.1. , , 19F, 13C, 29Si 31P.
. 1.1 , / > 1/2

. ,
1.1. ,

H
H
B
11
B
13
C
14
N
15
N
17
O
isp
29
Si
31
P

10


,
/
^N

1/2
1
3
3/2
1/2
1
1/2
5/2
1/2
1/2
1/2

Y.
10 - -
8

2,675
2,79277
0,411
0,85735
0,288
1,8007
0,858
2,6880
0,673
0,70216
0,193
0,40369
-0,28298 -0,271
-1,8930 -0,363
2,6273
2,517
-0,55492 -0,531
1,1316
1,083

, 1

Vo.

1 T

- ,
%

42,577
6,536
4,575
13,660
10,705
3,076
4,315
5,772
40,055
8,460
17,235

1,000
0,009
0,02
0,165
0,016
0,001
0,001
0,029
0,834
0,079
0,066

t
-
*

99,98
0,0156
0,003
18,83
0,111
81,17
0,036

1,108
99,635
0,02

0,365
0,037 -0,004
_
100,0

4,70
100,0
~~

.vv*

I
30

JL-I

20

10

<-J, M
. 1.8. - | 5 , 1 7
15N, 17O, 13C, 19F 1H 1,0 T.

, .
. , -
.
. ('KP).

^,
, ,
(I. 11). ,

[(/+I)// 2

(1.13)

, B0. ,
. 13C 15N
-

28


. -,
. VII IX,
.
. .

.
- | 5 1 7 ,
. 1.8.
,

.

23,
).

Il

.
.
- , .

5, , 6, 11 (. .

1.
- 1 5 , 17O,
. I, ,
. , ,
. -, , ,
. -,

, ,
-. ,

, ,
, , . ,

.
. , , , ,
,
(. II. 1). .
.
, 1,4 T

II

30

C 6 H 5 -CH 2 -O-C-CH 3

I
I

-
I
H

CT = (02/3)
.

V 0 = 60 , V 0 Av, Av
1 .
, .
H,
. BO *
,
, B0 (. II. 2). , . , BO 0, :
(11.1)

= B 0 ( I -CT)

*
ls- , 0
, .
k - $


. . 2. .

31

() dr

(. 2)

() ,
.
,
.
, , ,
. , B0. , :

= <7 +

(.)

,
,
. ,
,
,
.
(II. 3),

CT _ 0 I I
'
'

ft,

,
. , B0
,
.
, , , ,
. CT ,
() :

-C-H

. U. 1.

(II. 4)
'

< * < .
<* '. , ,

32

II

,
. ,
-.
. IV. , . , , , 26,6-IQ- 6 ,
< B0.
,
( ), .
,
- (. II. 1).

,
.
.

JJ

Si(CH3J4

500,0

433,0 .

_>

300,0
*t

I .
I -

Z-J J

1.1.
,
. ,
So v, . ,
S0 (, 1,4, 2,3
5,2T) (1.10)
. ,
. ,

, . . . ',
(TMC). j
, - \
. -|
60 , . II. 3,.
. -

- I

. II. 3.

116,0
*--

Jf^,

1
S


60 ; 6
.

, 500,0 .
( ) ,
,
.
( II. 3,6). , ,
. . , (1.10) .
2,3 T 100 , 721, 500
2

X.

II

34

193 .
, :

16

12

10

(. 5)

960

840

720

600

480

360

240

1600 1400 1200 1000

800
I

600

400
I

6 = (V1

H)/VO

VQ (, 60 ), 6-
(. .). , 8 7,21, 5,00
93 . . ,
60 1,4 T 100 2,3 T.
,
,
.
,
. TMC
.
,
TMC
.
. -
.
,
, .
, , ,
(, 1 /).
. ( .) 6- -. 6- ,
- TMC , -
10 . . ,

=10,0 6

(II. 6)

, -, . , .
6-,

, . . , . ,
,
, , , -

35

-2

-4..

I
120

I
240 (60 )

200
l

200

10

12

120

400 [

14..

(100 J

. II. 4. - -
60 100 .


. -, - .
6- -,
60 100 . II. 4
. ,
* , , , .
, , TMC. 8 , ,8-
, .
(. .), . Aa , .
1.2.

-
. ,
. II. 1. . , , .
, , ,
. . 5.
2*

II

1H
QH 5 CH 2 OCH 3 +

/1...
.!._
52

Zi^
I I i
8

I)
2)
3)
4)
5)

^A

1
4

1
3

I
2

29
28
29
29
29

43
43
42
42
42

64
64
64

65
65

Ii

f,

'

^,
,

'*

. *

5 : 2 : 3 . ,
.
,
. ,
, .
H.

COOCH2CH3

V? 4COOCH2CH3

.
, / ,

, ,
.
(/ AB) (MA/MB)
(. 7)
= (NB/NA)
N , , , MA
.

. IL 6 1 : 1,491 ( ,
).
2,2 3,2

__

23 .
/_

. . 5. . .

HCOOCH2CH3

C 8 H 5 CH 3

: :

^
^

32

I
4
21

37

*>
I
6

-/V
1
5

1
4

j
I

. II. 6.
S 6 . .; 60 .

1 : 1,519 0,030.
, (2 %)
(24%). . II.
, , , .
II. 1.
, . II. .

1.3. .

, , -, . . II. 7
,

.
- H CH3 > CH2 > CH. ,

ff

39

H
II

OO

CO

i s
1

CH3-CH2-C.
\

(L>

NH,

XX

*V

N/

^\/\

X
O
0>1

S
U
Cu
O
(U

(N

M/1

I^

c>- 1" ^]
x S^^z

C
C

Il

l "
3;
X O
11

ro

-x

-p

T
CJ

ZxO

. II. 8. .

1 g-I

C:

^
^~

**

in

I
O
O
C

CM

^
S

C
C
O,
U

I"
,

~
:

1
^<N
X
Z

(
m
I
O

d>
O
u

X
O

CD

X
O

O)

Qrt
O

^ Il _
O

ZIl

c-

I -E

H OD

I
-

g
O
OJ
*

i
O,

><
CT)

SQ

t~f

f~,

-r

CJ

CJ

-^

0,9,
1,4. ,
0,22. 4,0 6,5. , , , (CHz=
=), 66,5.
7,0 9,0. 2, , 5/? -, ,
, .
, 2,9. , , , , .
. .

, NH, NH2 COOH. , . , 1,4, , , 4,0. ,
, ,
. ,
.
. , COOH,
NH2 NH ,

40

1H

41

II. 1. ( )

CH3-CH3
CH2 = CH2
CH=CH
6
CH2 = CH- 3
CH = C- 3
3 3
12
31
212
13
32
32
32

3
(32)20
(32)20
323
323
323
( 3 )
(23)3
653
65

0,22
0,88
5,84
2,88
7,27
1,71
1,80
2,17
1,44
3,10
5,30
7,27
1,22
3,70
2,58
2,10
8,63
2,20
9,80
1,16
3,36
2,03
1,25
4,12
2,12
2,42
2,32
9,96

9,78
9,12
4,16
7,12
2,73
8,29
8,20
7,83
8,56
6,90
4,70
2,73
8,78
6,30
7,42
7,90
1,37
7,80
0,20
8,84
6,64
7,97
8,75
5,88
7,88
7,58
7,68
0,04

(. II. 8).
. II. 1
- -
,
.

32

27

74

11.5.
:
CH3
CH3
) CH3-C-OCH2C6H5

. 2.
,
: 10, 18 36 87,27, 5,30
2,17
?
. 3. . . 9
, .
. II. 1 .
. 4.
100 62,32 67,10 3:5. ,
60 ? , CyH8?

CH3
CH3

) CH3-C-C=C-CH3
CH3

a') CH3-O-C-C6H4CH,
CH33
CH3
') CH3-C-CH2-C=C-H
CH3

, TI m
,
I ' 0 .
: ,
. C0H4(O.) [(2 + 2) 6]/2

2. -
2.1.


. 11.11,
.

C6H8O

^3MgU 2 Ui

4-

1
I

-/

C4H10O1

4-

I
8

I
4

I
3

l_
0

C8H6O2

f
2

. II. 10. ( II. 6).

'

"

Il

44

}
-CH,

C6H5-

, - , .
- E
X
,
(I. 5)

-CH,-

= /11
(II. 8)
IA Ix
, a /AX - . (1.5) ,
. ,
- /CAX:

-CH,

Il
HC-

HCOOCH2CH3

-CH1-

45

. II. 11. .

. , . .
- .
,
, , . . II. 12 .
, X. , X
, .
, , X,
. . ^ , . , -

*AX = 0/Y A Y X )/ A X
("-9)
,
-
, , .
" (II. 8) , - , , *
- . ,

J
4 f opfiumasieit
. II. 12. -
.
HF; CH2. .
. , . . ,
, . ,
, .

46

II
MP W

. -
.
S0, , - . -

, , .
, - ,
. - (J = O)
4
B0. , , S0; ,
, ,
(. . 13,). Ai 2
, , ,
. - (J^ ), ,
.
, / >
,
. , . II. 13, .
, Ai A 2
,
.
-
AX, . - X, , , ,
,
E () = V(Tn 7 (O + Z S ////( M/)
(H. 10)
'
'</
( ) VA VX - /
1) E1 = (1/2) VA + (1/2) YX + (1/4) /
2) 2 = ( 1/2) V A - U / 2 ) V x - 0 / 4 ) / A X
3) E3 = -(1/2) V A + (1/2) V x -(1/4)/AX
4) 4 = -(1/2) VA-(1/2) v x + (1/4)/AX
AX - ,
, (1/4)/ ,

AX

(D

IL

CZ)

If

ft

ft
J #0

. II. 13.
.

-
; 6 - .


. (/>0). (2) (3)
, (1)
(4)
.
.

Ax

A2

Ai

A2

. / = 1 ( / = Z/ mi (O
),

(3)-^(1): ,-3=vA+.Cl/2)/AX (2)-*(l):1-'2=vx + (l/2)/AX
(4)->(2): 2-4=vA-(l/2)/AX (4)->(3): E3-,=vx-(l/2)/Ax
, VA Vx
/AX- -
, *
,
. II. 13. ,
. , - /
, , ,
. ,
-
, . , .
, - , / , ,
.

48

II


- / , , . , ,
*
,
. IV. ,
, .
2.2.


(. 11.11). . , . . , ,
. , m/(t)
.
, :
2-

OO

Pa
PP

"T

+1

TW-T.

49

1. 7 = 1/2 + 1 , . ,
, . , , .
, HM
Hx, HM .
,
/AM /MX .
2. ( ) - .
3.

1 :/\ :( 1)/(2- \):( \ ) ( 2)/(3-2-1)... .
=0
1
J ...
1
1
2
3
4
5 '
6

1
1
1
1

4
15

3
6

10

5
6

1
4

10
20

1
5

15

1
6

1,

^
^aP
PPP

+3/2
+ 1/2
-1/2
3/2


, . . *
, ,

.
1 : 3 : 3 : 1
. .
, (II. 10).

4. - , . -

, .
5. - . -"
,
.
,
,
. II. 12.
CH2 CH3 , .
.

.

Il

50

51

Jbc

CH2-CH2-O' CH3
(6; W
()
8,8

8,6

8,2

7,5

7,3

7,1 S

. II. 15. - 2,4- 100 . he =


= 9,1 , 1 = 2,8 . J ( 4).

V^V-CH2-CH2-CH2-Br

()

()

()

D
(C'
()
H3C-CH2-CH2-CH2-O

*
CH3

8
II 14 . --1-
.

.
. II. 14 .
. , . .
,
.
,
. .
. II. 15
2,4-. 4, /
. : / < } <
<Jbc-

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

52

II

/n/ = +1, 11 .
( W), - , N = 2/ + 1.

50

II. 7.

10

I Il I

Mi Mi
100

. . 17. NaBPVCeD 5 CHD 2 ,

14

15

NH* NH4 ( II. 9).

, , I6. - 2 3 .
1) CH3-OH;
a
b

2) (CHs)3C-CH2Br;

4) CF3-CHF-CH3;
a

. II. 16.
( . 8).

be

3) CH3-CHCl-CH2-O-CH3;

5) (CHs)2CH-O-CH2-CH3;

6) CHDCl 2 .
a b

II. 8. . . 16
,

54

II
1

. H
A, M X. - /AM,
VAX /MX, ,
.
II. 9. . II. 17 NaBH 4
14
15
C e H 5 CHD2, NH+ NH*.
,
- .

2.3.

2.3.1. .
,
. ,
,
- . ,
,
.
, .
: - . ,
- .
. ,
. . . (. . 1, . VI).
,
. - CH2 -
, ,
.

. II. 18.
-
6--4--2,4- (-) 0
-2,4--1 90 C
220 ( [2]).
-

.

.
- .

,
(. . 18).

. 1,1- (1), , , , - . Ji,s ^f= / ( 1 =^= !)
(2)
- /i >3 /1,4.
- -
. , (3) , (J\,a = /1,4 == /2,3 =
= /2,4).

, - , -

"V


. '

S6

Il

1H

1,1- . II. 19.


(. II. 19,), , ;
, (. II. 19, ) . - , . V.
,
. , 66,37 7,42'
(. II. 19,). , , , - - - 7=3,2 . - . ,
. V.

"\> U

. II. 19.
1,1- ( [3]) () ().

(),

(. 1 . V), 1,1-<
'', A 2 X 2 .
, ,
, .
,
- ,

, //VoS < 0,1
(. . 2.3.2 ). ,

2.3.2. J/v08. , *
, ,

vo8 () ->
.
. vo6 , - ,
,
(. 11.20). ,
. ,
, , . . - . , ,,
,
.
, ,
, .
-, .
//V(A , 7/vo6 <
< 0,1 .

II

II. 2. -
()

I I I
CL Ct Cl

\ /
12-20

=c'

\/

03,5

614

1118

-IO

410

C=C-

3-7

_L

-60

V/

-
-120

23

1OTu.

. 11.20. 1,1,2,3,3- 1,2,3-.

-H6-

//v06 0,06, 0,7.


.

, .
, .

. . . . IX. . - .
,
' , . IV.

-
_ 13 , .
2.4. -
.

,
, - < H H . . II. 2

5-12
= 2-3
=0,1-1

H6
H3
^ = -13
/? = 25
/ = 25

- . ,
- 517
,
, . . . -
. JTpaHc , /.
, Jaa > Jee- C
, , 1 < /. , H H H N H , .
- ,
-.

, -
, -
.
, ,
(. . VIII).
11.10. . 11.21
60 , - . 1.
. 2. - .
3. , - ,
. ?
II. 11. . 11.22 H0 Hs
90 .
- .
11.12. . 11.23
. - .

C 3 H 7 Cl

C7H8S

O S

. 11.21. ( II. 10).

62

II

III

10

.
.

1.
7,36
j

8,77
j

. 11.22. Hn Ht ( II. 11).


'

20,
~'

7,47

2 ,
3/4

6,63

6,17

5,37

. II. 23.
11.12).

5,15

( -

*
1. 71.
2. Kessler H., Angew. Chem., 82, 237 (1970).
3 , . 92.

, 4, 7, 17.
* ' .
.


. , ,
, .
,

.
, ( 99,8 %). 90 % , : -de, -de, ^, ^6 D2O.
. III. I.
, -
- . ,
, SbF5 +
RF-J-SbF5-^R [SbF6J"
, . .
SbFs. , ,
; ,
- .

III

64

III. 1.

T.
.. T.
.,
0
0
C
C

-d

-de

-ds

-de

1,4-

CCl 4
CS 2
CHCl3
CDCl 3
CH3SOCH3
CD3SOCD3
CH3CN
CD3CN
CH3COCH3
CD3COCD3
CH 2 Cl 2
C4H8O2
CgHia
CeHg
C5H5N

H2O

CF3COOH
SO2

^- 1

76,8 -22,8 -0,684


46,3 111,5 0,681
61,3 -63,5 0,733 7,27

2,73

189

18,4 0,609 2,58

7,42

82

45,7 0,486 1,95

8,05

56,5

-95

0,460 2,05

7,95

-95,1 0,733
12 0,589
6,5 0,631
5,5 0,626
-42 -0,612
0,0 0,721
100
72,4 15,3
10,0 -75,5 0,812
40,1
101,5
81,4
80,1
115,3

5,35
3,68
1,43
7,27
6,9-8,5
4,8

11,6

4,65
6,32
8,57
2,73
1,5-3,1
5,2
1,6

, ( 0,5 %) , , .
. III. I. ,

X
3

'

H2O

65

0 5

. III. I. -


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

^
, ,
, . , .
..

. III. 2. -.
;
; .

"

, CHD2;
, - , 2, 1, , 1, 2,.
1 : 2 : 3 : 2 : 1 . *, 1H ^
,
.
, 2030 50
5 (. III. 2,)
, 0,5 .
34 .
(. . ), . (TMC) 0
(26 C) ;
.
5 % (.)- TMC .
, , . , TMC
, ,
.
, . 1,4- ,
*
. .
X.

H,

H 2 D.

66

III

67

3- ()$1
CD 2 CD 2 COONa (4),
6 = 0,00.
,
.
, , ,
.
. III. 3.
.

2. .

, M , 0 , 4-10- 7 --- 2 -~ 2 . M
, . .
=
(III. 2)

Xu , , . %0 , . -

,
. ,

. , , . . ,
,
(. 111.2,6,),
-

. , ,

. 8

: = 7 : 5 ( );
.


S , , :
B = U0(H + M)
(III. I)

6
= 6
-4- ^- (
"
" ' 3 V

CH2OH

(III.3)

-;
-]

. -, ,
1 . .
,
, .
, , , -de.
( 20 % .) 4,96 . .
CCl 4 5,80 . .
0,84 . . , , (. . 1.7 . IV).
- - , 2,31(7,274,96) 1,47(7,27
5,80) . . ,
(. . II. 1): , , , ,
.
, - , , ,
.
,
. ,
*

III

68

4a-CH3
4/- 3
-19

-18
-18

1
1
1
1

1
1
1
1
1
4
3
2
1
0
5
4
3
2
1
0

1
. III. 4. H 4,4--5--3 () () (, [I]).

CH2OH ,
AB 2 (. III. 3). /(CH 2 OH) . ,
,
.

.
- .
,
. . III. 4 4,4--5--3.
.
- , *
, . , (5) 1--2- (6)
7,6 9,9 4,2 6,3
.
\
.C=N
H'

Cl


-,
NH NH2. , -
H-C-O-H, C-N-H.
, ,

(. . VIII).
3.

, ,
. .

(. . III. 2 1.5). ,
B0, .

H
4

'

69

OC2H8
c

- 111- 5. .
; ; ;
( ~ 10 ./).

HI

70

71

<

SUBHUU
/()

^
8
z

0,5 /

!--0/5

0,02

. III. 6.
!/-; ;
!/- ;
-.
0,45 (60 ). , .
, .

. III. 5, ,
.
(
) .
.
, ,
.
, , , .
, , -, - z-,
. , TMC /- ,

0,04

0,08

0,16

0,32

. III. 7.
.
; ; -; 0,32
, . . W = A T , , (. . 3 . I);
.

,
( , *), .
(. III. 6, , ).
,
.
. ,
(/-, ,
. III. 6, .
, ,
-.
(. III. 6, ).
, , ,
, . . .

, wiggles

72

III

433,18 ,

401,8,

. III. 8. 6,6--2,4- TMC (


). ( [2]).


, .
, , .
, -
.
. III. 7, . . VII.
.
. ,
. , CH 3 (CH 2 )
CHO ,
> 20. ,
.
, (. . VII).
, .
, ,
, . .

73

436 727 60 100 .


,
;
. , . . ( ) ,
(. III. 8). ,
, , 0,1 .
, , .
-
. , .
, .

. , , - , 1 ,
.
4.

,
, 2030 , , ,
-. , .
(. . 3 . I), , .
, Bl. , /,
(. III. 9), 25 : 1 50 : 1, 60
100 , . . 1,4 2,3 T.

t, -

74

III

<\/t ,
t.
, , , ;
.
. , . .
,
.
50 . ,
, , ,
,
, / .
t ^Jn,
(. III. 10).
1024 ( ) ,

. -

75

H9

\^^
/1 = 5

CHj-O-CH2-O= 58

.-

. III. 10. CAT 0,2 %-


4- .
(. 1.3 . II);
; 250 .

*. ,
, ,

. , , ( ).
,
,
.
--,
. VII IX.

. III. 9. 1%- .
/ S
N, -( )/2,5.

5.


.

* CAT , ; computer of averaged transients - . . .

76

III


, , , . . VIII. ,
,
.
, , 170 +20O0C- ,
, , ,
. . , .
.
,
.
, . , ( ) ,
,
-10O0C.

, -
.
,
, .
A V ( B )
CH3- 2-, , ,
, -.
(III. 4) (III. 7), 60 .

77

, 0,50C , , - , (0,03 % .) .
, 100 +14O 0 C , . III. 2, ;
.

.
.
, , , . ,
. , ,
-dis (7) 2080C, 60,327.
"Si

DaC-Si^

I
t

D 3 C H2 CD 3

-de (, ),
10O 0 C. 10O 0 C ,
.
, COS (
0
138,5 138 C ).
.

, :
175-225 ; T = 537,4 -2,380 Av
220-270 ; = 498,4-2,038 Av
265-313;
= 468,1 1,810Av

(III. 4)
(III. 5)
(III. 6)

, :
310-410 ; T = 466,0 -1,694 Av

(UI. 7)

* .
.

1. H., . : .
. M.: , 1966.
2. Hinrichs H. H., Dissertation, Cologne, 1967.

78

III



) Laszlo P., Solvent Effects

T. 3.

and Nuclear Magnetic Resonance. . 74,

) Ronayne J., Williams D. H., Solvent Effects in Proton Magnetic Resonance


Spectroscopy. . 73, T. 2.
) Deutsch I. L., Poling S. M., The Determination of Paramagnetic Susceptibility by NMR. J. Chem. Educ., 46, 167 (1969).
r) Loliger J., Scheffold R., Paramagnetic Moment Measurement by NMR. J.
Chem. Educ., 49, 646 (1972).

IV

-

. II , - , , .
, , , .
,
. . , . ,
, .
1. ,

. II. 6. , . 1 . II,
.
, , Is- 25-
. : 1)
* ; 2) '.
. -, cr*,
. , ,
B0 ,

IV

80

, . . ,
.
, . ,
:
=

+'
+ +' 0
(IV. 1)

"+' "
"'. ' "^BB

,
,
.
1.1.
, ( II. 2).

, . . , = 17,8 . .
ls-
, .
, , HF <
< HCl < HBr < HI. .
1.2.


.
,

.
. IV. 1
, . 8,
, :
6(CH 3 )

E ( )

CH3F

CH3C/

CH3Br

CH3/

4,13

2,84

2,45

1,98

0,13

4,0

3,0

2,8

2,5

2,1

X CH3X. . IV. 2. ,
X = Hg, Sn, Cd, Zn, Al, Mg Li
-

81

2,0

II
S

CH3X

CH 3 M 2 X
W 3 CH 2 X

J
2

>

L_
2

>5
3,0
3,5
4,0

- , , ,

9, 12, 15, 18, 22, 35 43%



?07r TV 3 If
(. IV. 3).
fifCH ? 1 [6(CH3) 0,91;
345 072 * 1 2 ,
Hg
t

Tl

Cd Zn
1 1

GQ

Li
I

Mg
_

Al

Pb Ge "si

S Se

Cl

Bi PAs s b

N
_

Br

IV

82

83

O 2 NCH 2 CH 2 CH 7

-CH 2 -NO 2

. IV. 3. 1-.

,
. IV. 1, ,
. ,
,
,

. ,
(. IV. 1). , .

H X, , . 0 .
, H ,
. - , 0 1,90 +1,90, 1/7 1/5 1 .

0,7

0,8

0,9

1,0

1,1

1.2

1.3

Jf-

. IV. 4. -
.
> 9,54
0,993 0,65 . .


- (. IV. 4), .

ACT =10,0 Ap
(I V. 2)
Aa , - . ,
2 - H.
, ,
.
.

5( H) 9,17

7,27

5,37

&

-
-

IV

84

85

IV. 1.

/ 5 10,3

0,5

|
CH3

65,06

13,50

CH3Li
6-1,3

CH3

,
- - . Ap, ,
Aa (. IV. 5). 12,7.
, . IV. 1 . , ,
.

-. ,
, ,
. ( ,
) -]
, , ^:
. , , -

1,88 1,01

62/6 6,28 2,46

(CH3)2N[g
1,3

(CH3-CHJ2Mg
1,26 0,64

(CH3-CH2-CHJ2Mt?
0,90 1,50 -0,57

. IV. 5. -
-
= p(CeHsX) 1,00 ( [2]).

3,15

3,07 \=

-0,02

[CH 2 -CH-CH 2 ]"

CH2-CH2-CH3

6 1;2

H3C'^^&^^^CH3 63,33

-0,04

"7

8,97 9,64 8,97

64,35

CH3-CH2Li
1,33 0,99

-
on-

[CH2-CH-CH2]^

CH3

68,02

CH 2 Li

N(CH 3 J 3 ,,

8, 80

6 ,09

7, 98

7, 97

6 ,30

7, 66

5 ,50

7, 60

8,45

. .
-,.
,
. , -
. - /-. - -,
/-. - , - > > .
IV. 1. ()
() -
, (IV. 2) 6 7,27
. .
'2,7 . IV. 6.

1,000

1L020

/-0-CHj
1,018 \
\ =/

0,94 0,95
'

81

C6H5

\\ //~" \
C6H5

IV

86

, -;
, , , -'
, ;
/0. , - ".
, ]
, .*
1.3.

ls- '
, . , , -,
, !
, .
AB.
BO |J,A,
,
( XA
,
(*), () [XA(Z).

)

Z
1=, , z

Xl(I-3cos 2 8 2 W

(IV.

6 \i^(x,y,z) Al
a R . !
4

87

0,3 HM

0,
. IV. 6.
.

B0. , ,
, , . . .
() , B0 .
B0, .
, . (IV. 3) (1
3cos 2 6), , > (#)
XA(Z) XA , Ao .
-. XA
, ,
.

A)C = X 1 1 -X x
(IV. 4)
-:
= (1 -3cos26)/ 12/?3
.

.
. IV. 6,
, R = 0,3 HM

IV

, 9 = 90 . A^ 140-1O -36 3 /. , (IV. 5),


(. IV. 6, ). (Aa = O) 54,7.

- . J
"
, <

, CKO-;
- ;
]
(. . 2.3 . V I I I ) , -;
. 0,5 . . , H3 ,'
.

. *;
- - (8 861
). , ;
, .
OCH 3 5 3,78
5,18

HOH2C

Sa

, !
" -,
: ,
,
.

C=C C=O,
C = C C = N.
, ^
. . IV. 7, |
, -"
. ,
,
.
(. II. 1)

89'

-.

'

;.::=|||:

. IV. 7.
.

-H
'

C = C. , , ,,
. 4- (9). H (5) >
1,71 . . .
.

, ,
(- IV. 7, ). - ;
g
.
C=C C=O , . ,
, . IV. 8.
, 10 11 , . . -1,3,5 (12) (. . 2.3;
. V I I I ) . -

. IV. 8. ;
- , .

IV

Cs=C4. , ,
. , ,
(IV. 5), , . ,
- (13) , -. , 13 136,
.

91


.
( . 1.6).
C=O , -, (16) (17)
H

2,09 5 0,23

--0/2H^

5W

,^ 2|

peHs

1
C6H5

11

IO
H 51,03

51,32//

53,S3 H

13

12

13

H S 3,7S

135


j
-1
C=C, H J
. '
]
-1,3 (14), -;
s-, -;
]
1,1,2,5,6,6--1,3,5 (15).
.55,16

185

,^-
186.
- . (19)
,
. (20) (21).
, ,
^-, - ,
C=O. , -2,4--1 (23)
//COOR

//COOR

KOOC
67,10

19

H
56,83

20

66,28

21

22

65,06
H

18

14

6 6,27

2 1,007

6 6,62

15

= CH 3

3 0,969

i. 1,004

5 0,986

5,93
7,07
6,28
6,38

COOR

92

IV

V
I:
N
/ \

V
I;
N
/ \

- ^

OH

I:

II
r

N
X \
4
C
C -V

e^i

/\

C^.'

. IV. 9.
( . [3]).

, - . , H2,
,
, H3
.
,
, ,
. ,
.
. IV. 9 . , .
(IV. 5),
, ,
.
, , H, C = C (- = 90,
AXC-C=HO, AXG=C= 340-IQ- 36 3 /), .
IV. 2.

5" 6,11

V" "Y
A

5- 5,29

6,52 3,7A

H^
6,63

^C
g

LlX^ ^^ <'

3,9^

5,81

H
6,21

5,94

H x ^H

CH, I

93

OCHI

'il^X^^^^

l-r ^CN
5,46

8
^

\ V
. IV. 10. .

1.4.
-

, ,
.
,

, .

, -
, -.
BO, . , ,
,
B0

(. IV. 10). , , . , .
, ,
. , B0, - -
= 0 /4)( 0 /2 )

(IV. 6)

, B0 ,
w e , .
-
2

/ = / = (/4) ( 50/2)

(IV. 7)

, .

94

IV


= / 2

(IV. 8)

, (IV. 7),
= (/4) (3e2fi0r2/2me)

(IV. 9>

95

. ,
, R
, /R3 , (II. 1),
' = - 0 = (/4) (3e2B0r2/2mefl3)
(IV. 10)

= - (/4) (22/23)

(IV. 11)

1/3
, B0 .
, ^0,
= 0,14 HM, R = 0,25 HM, =1,77-IQ- 5
6 = +1,77 . . -1,3 (65,8) (67,3).

, -
, 2 - . ,

Bn
-, .
, , .
'
. ^
,

. , , -
, (IV. 5), % =
= 630- -36 3 /.
,

Hr

9,0

H*

8,0

7,0

. IV. 11. R, .


, /?3. , - , -,
-, -
. . 6 Y > 6 > 6g
(. IV. 11). (IV. 12):
= - (0/4) (eV/2/) Z 3
t

(IV. 12)

IV. 3. ( ) H4 , (IV. 5).

96

IV

, , , ,

.

, .
, ,
-. 1,6-[10] (24), -15,16--15,16 (25) [18] (26).
H

97

(JlL

\2rnL'

-4-

| *

-16()1,2; 6,95
v
6 (CH 2 1-0,51
(), -8,67
6(CH 3 ) -4,25

9,28
-2,99

24

26

4 + 2 - ( = , 1, 2, . . . ) ,
*
. -

.

. .

- 4? .
, ,
. ,
, ,
.
(4 + 2)- 4--
. -

. IV. 12.
.

L. , , . , . I
. , L, L = qK, ^ = O, 1,
2, . . . , a q
, :

9*0

<7=*1

</s*2

=
^= h/K,
E = mv2/2 =P2/2m = h2/2mK2 = /2/nL2
(IV. 13)
,
, , , . IV. 12, .
4

X.

98

IV

25

27

12

-A

-8 5

. IV. 13. 25 27 14 16 - .


- ,
, , . .
.

(4/ -f- 2)--

(. IV. 12, ) , ,
.
4-- , (. IV. 12, ), .
, [4/]
. , , ,
.
. (. I V . 1 2 , )
.
, (4/ -|- 2)--.
BQ
, , . 1 . II,
. ,

99

, . , [4]'
, , . , ,
, .

, . 25

27, 16 -.

621,0, 6
3,2 4,0.
(4/ -f- 2)-- 4/--
. IV.13.
, 28 29, ,
[4 +
+ 2]- [4/] .

7,20-7,86

2,07-3,65

28

29

30

& () 5,7 - 6,6


5 ( C H 2 ) 1,5,2,3,2,4, 2,7

31


. , -, , 12-
.
, - ,
-
. , ,
(30), 5,80, . . , 4*

100

IV

CH2

. IV. 14.
[14] 31.

60

-30 F

1,6-[10] 24

1,6;13,18---

/=12

.
IV. 15.

/
. (, [4]
, 3 - .

, 1.
. M
-.

101

-1,3. . 1,6;8,13-- [14] (31)


1,6-[10] , ,
31 , , -.
(. IV. 14) , . , CH2 10-
, [14] AB ,
-1,3,5. ,
, , 31 , 24. ,
6, 7, 8 13, 14, 1 - , 2 - ,
, -,
,
. .
. IV.15 / - ,
. ,
, ,
, , 4/- -. . IV. 13,
27 , 25. ,
-
6
1 . ., 25 23 . . 45 . ., 27
910 . . 20 . . .
,
1,5 . . ( IV. 2).
1-5.

,
, . - ,
C-H ,

102

IV

103

5 5,0

1.6.

5,1
5,2
5,3
. IV. 16.

Ht,
(, [S]).

5
-60

-30

+30

+60

+90
0

C >

,
(60,22),
, .
32/33 34/35 . . IV. 16 Hs
. s-- , (36, 37) .
Hj, , s--
, . &
.

6 - 5,58

32

5 = 5,43

33

6 = 7/2

= 6,91

34

35


, .

, H. ,
H , .
. IV. 17, ,
N ,
,
.
= - AE, - BE2
(IV. 14)
H, a E2 (

, , 2-- 12
10~18 , ).
(IV. 14) -, - -
: 0,70, 0,19 0,14 . .
, (0,97, 0,30 0,45 . . ).
,
, .
.

36

37

. IV. 17.
.


104

105

IV
2,00 M. .

, (IV. 2)
(IV. 14). H,

, , ,
Aa =-0,126 S (Ap,/'R!)COS Qt - ,170 (Apt//??)]2

/
Z
3 /

(IV. 15)

Ap,- f, Rt
i H ( HM), 9 H
t H.
IV. 4.. , (IV. 16), . 0,140 HM () 0,110 HM (H). .

>

\\
^-
1

'

98

0,829

'

1.7.

kNJo,899

I 1,520

UO?

,
(IV. 14) BE2,
--,
( ). . (. 1 . II),
. 3840 .
4--\..
I
//H
HW UOH

4*-2,..

. IV. 18.
( [6]).

r^fi 0,927

^^'.
W
N^ 0,952

20

60

. 1.3 . II, -
-,
. ,
, , .
,
. . IV. 18, .

0,92

//OH
H-J \-H

Cl

R-C=N-

H-C-Cl
4

Cf

41

38

88

39

42

106

IV

CH 3 -CH 2 -OW

1.8.

. 1.2 .

- .
. IV.20,
, ,
23 . . . ,
,
. . IV. 2 .

. XI. 1 .
,
. , < , 30 . .
, ,
.

12

11

107

10

. IV. 19. ()
5 %- ().

(. . 1.3), 41. . IV. 18


, . ,
- . 42 .
- ,

.
. IV. 19
.

3,5

3,0 5

. IV. 20. .

108

IV

IV. 2.
-
5 5,30

5,37

^7V
iW

90

<(JVw
'XL/

; "
Fe(CO)3

'

Fe(CO)3

7,37 7,53 6,09 5,48

6 3,08

Cr(CO)3

\
Cr(POI

KJrRu(CO)2 W
/2

Cr(CO)3

F.

5-6,3

O -12,3

'XVX^Y

WW 3+

^'^

NJS/

7,07 7,30 7,49 5,68 4,92

5-10,5

-2,1

/~
\
I /' 4--Mo(CO),J /I W

I x\ >v/

S -28,1

' J

* -18,6



. . IV. 2.
-

. , .

LJ

U T)

6 4,94

1
L.

4,18 2,67
f~f

109

1.9.
, , . 1
. , , , . ,
, ,
,
, .

. , , , , ,

.

,
. -

, .
.
. .
1 . . . III

. , , , .
, , ,

. ,
,
-.

IV. 5. ( [7])

1.10.

,
.

5 ( 8 ) , , .
, ,
5 ( 8 ) ,
. 5(8) .
1.10.1. .
, 8

= 0,23+ Z 5 ()

(IV. 16)

5(6) . IV. 3. ,
,
(IV. 16) 62,76, 5,29
7,82 , 63,1, 5,3 7,27. IV. 3. 5(6)

Cl
Br
I
NRR'
OR
SR
CR=Q
CR=CR' R"

S (6>, . .

2,53
2,33
1,82
1,57
2,36
1,64
1,70
1,32

3(6), . .

C=CH
C=N
CH3

OCOR
COOR
CF3

1,44
1,70
0,47
1,85
2,56
3,13
1,55
1,14

-CR3

=
-OCH3
-OCH2CR3

0,248

-C2-C3 0,244

/C 3
-C2'
0,147

1
2

3
1
2
2
3
2
2
3
1
2
3

S (6), . .

-0,038
3,802
0,583

-OCOCR3

0,203
1,032
0,694
1,021
0,004
-0,374
-0,237
0,210
2,467
0,048
0,235

-F
-Cl
-Br
I
-NH2

2
3
2
3
1
2
3
1
2
3
1
2
2

6' (6), M. ,

2,931

0,041
0,086
0,089
0,131
2,170
0,254
0,177
1,995
0,363
0,023
1,846
0,388
0,094

4,22, 4,70.
5(6), . IV. 4
IV. 5, .
- ,
, 1. (5- . IV. 4, 5(6) . IV. 5.
, ,
= OR.

(IV. 17)

6 = 0,933 + Z 5(6)

.
CH3-COCO-CH3.
1
2

: CH3-CO-CO-CH3 25(6):

C 2 -C3
=0 C 2
=
-CR3 C 3

IV. 4. S (6) (. .)
( [7])

-C2

111

IV

/C3
-C2-C3 0,00

+0,244
+ 1,021
+0,004
0,038

+ 1,231

6(CH 3 ) (IV 17): 6(CH 3 ) =0,933 + 1,231 =


-- 2,164. 62,33.

oooooooooooooz
: -- z
"
Oi-:"

.^W

Oi

,*-* 1-1*

_j P1

< tO J5

eg

f**i f>j (^ ^j ("*!**

*=;

X KD

Sg

5
S^o*

S
EQ

(DOItOi-Oi

? g S
Ca ^

1 < *. 1

I I I

-~

/\\

fe

\. J

P *>

5
/Ti

>~j

.__.

^t

1-

"!

"

tB Ox S

a s= n >$

+
I +++
_ _
"

^k
E

">4^
to
S
OO

"(

=S
1 Ig

S Ss
E
g
S
*1
<
S

< O O

+0,

,
Vg

? ~1

S
2

tafa
I
sg

^
>
CT


1,84.

- S
0\ I=I Sj S

_,

P
l
|

o"o"o"to ""-

?.

S S

^
.
OO

*."(o

1 CU N3

IV. 7. 5(6) (, [9])


S (6), . .

H

()
-CH2O, -CH2I
-CH2S
-CH2Cl, -CH2Br
-CH2N

-C = C
-C = N

-C = C (.)
C = C (.)
-C = O (.)
-C = O (.)
COOH (.)
COOH (.)
-COOR (.)
-COOR (.)

0,44
0,71
0,67
0,53
0,72
0,66
0,50
0,23
0,98
1,26
1,10
1,06
1,00
0,69
0,84
0,68

0,26
0,33
0,02

-0,15
0,12
-0,05
0,35
0,78
-0,04
0,08
1,13
1,01
1,35
0,97
1,15
1,02

S (61 . .

0,29
0,30
0,07

-0,15
0,07

0,23

0,10
0,58
0,21
0,01
0,81
0,95
0,74
0,39
0,56
0,33

/
-4

1,03

0,97

1,21

1,37

0,93

0,35

1,10
1,18
1,14
2,09
1,35

1,41
1,06
-0,65

1,28
1,05

0,37

0,10

1,00
1,04

0,19
0,40

0,03
0,55

/NR2
C=O
/Cl

-C^O

OR (R .)
OR (R .)
-OCOR

-Cl
-Br

0,40

0,99

0,67

,P

NT

(R .)

-1,19

-1,31

2,30

0,73

0,81

1,00
1,58

0,24

0,04

0,69

-N^

(R .)

R
-SR
-SO2

1,15

0,95

" .; . ; .. R . R . , .
, .

IV

114

0,09 . .,
0,06 . . 3- :
Br

(HJ = 7,27+ 0,22+ 0,95 = 8,44


6 () = 7,27 + 0,22 + 0,33 = 7,82
6 () = 7,27 - 0,13 + 0,17 = 7,31
(HJ = 7,27 - 0,03 + 0,95 = 8,19

1.10.3. . . IV.7 5(6) ,


.

6 = 5,28+15(6)

IV. 8. -

)c

3fJ

4
5

H'/


(68,38, 7,80, 7,36 8,16 ).
, , ,

. ,
opro- . IV. 6 6 8,08, 7,66. ,
,
.

(IV. 18)

1.11.

. XI. 1 .
, .
2. -


- HH .:
. II ..2.
, .
, '
- ,
,

115

)c=

H'/

H4
/H'
\C C/
H4

/H'

\c=c/
HN4
c=cx

- :
H-C-C=C-H'
HC=CH'

(. IV. 8).
/. ( ). , -
, . - ,

.
, 3J 5 /
, a 2J 4 / , .
- , , . .
2.1.
-
(2J)
-
'/HH , 276
,
2
- /
- ,

23 + 42 . 2 /
.

116

IV

2.1.1. 2/ . $ 3 - 5/7 2 - 12,4 + 2,5 .


.
2J 5,0 ,
(. IV.9).
IV. 9. -
2 / ()

2=(

'H

IV. 10.
- ()
1. -

P CH2

5,5

CW3CI

- 10,8

RN=CH 2

16,5

CH2CI2

- 7,5

O=CH2

*42,2

/~

*2,0

QCH,

* 1,5

^O
. )2

HN

PCH2

QC0)CH2

\
/"
>=<
H

* 2,5

=(

- ,2

H
-11...-15

-12,4

CH4

'

2. fi-

,2,5

-4,3

<

117

-5/

2.1.2. . 2J
-, -.
. IV. 10 . ,
2 / .
$ 3 -
.
.
. . sp3
H.
2 / 1,3-
.
- - 2 / 2
. J
. , -

H
H
>=<
H3CO
'H

)=<W
Cl

- 1,*

2,0

R2 P
- 20

Li

\
/"
;=(
H

3. -
CHfN

- 16,9

CN-CH2-CN

- 20.4

2 / ,
-f- 7,1 . -
- .

, . , 12,4
20,4 . , -

, .
,
-

2JHH
" C-H.

.
IV

118

119

V,

. IV. 22. CHa.


30

. IV. 21. - !
2
/ - ( [101).

. IV.21. ,!
- -|
. -1
2J (43), (44)*
KOH-J
(45).
-11,6

2.1.3. -
2J.
- () , VHH. ,
/ - ls- :
/HH- nhK
(IV. 19)

**"=- 4 Z
-21,5

(IV. 20)

cih, th' .. ls- ' Wi 1F/, , , :

43

-15,9

45

44
2

/
, <
HH,
yrj
.
, <
**
.
'/iai
(. . 2.3 . X).

^i = C^A + '^ + + CIN#N

(IV. 21)

Ei EI ,
.
- , ,

i /.
2
" : ls- ,
S 2
P - 5/?3-.

IV

120

, . IV.22. ah, cih> . . .



Wi 4*4 , . . . ,
av s ( Wi Wi) ( Wi -Wi).
4 .
W\ ^2 . (IV.19) - -

D i /.
Cu1, clh; cjh cth' j
:
1
: W1 W3;
: W 1 W 4 ; +
: W2 W3; +
D: W 2 W 4 ;
, !
, ^
cifl cih'. , ,
|
2 .
av. - -*
W\ ( Ws ),
-
Wi ( W 4 ).

V1

Tf

!- *
Wi
. CIH C
,
, !
. \ \

121

. (IV. 20)
(IV. 19) , . D . E3E2
, 4 EI. 2
J .
(. IV. 10). ,
-f- /- .
, , S, D
. -

. (.
IV. 10, . IV. 21).
-. /-

CH2 . 2/. , - 2J.
Ws
COs^, z
.
2.2. -
(3J)
- .
, 3/, , ?
, , : 1) - (); 2) R^ (); 3) 9 0' (); 4) R H ().
H

122

123

IV
IV. 11. - ()

H3C

CN

H3C

40

60

80

15,8

100 120 140 1 6 O I o O '

12,3

3,9

. IV. 23. , 3
- / .
; .

(2Vl

2.2.1. . -
. . IV.23. (IV. 22), ,
4,22, 0,5 4,5 . / = + cos + cos 2<j>
(IV. 22)
,
HH. ,
3 / = 180 24 ,
,
3
/i8o > 3/0 .
(IV. 22) /4 = 7,
B = 1 = 5.
(. IV. 11). , - - , -.
- -. 1,2-
/ < J. ,
(Jaa > Jea ~ ]). . , -

/2

9,0

-12,0

13

3,2

12,3

3,8

11,2
8,0
COOR

/ 3

//*
9,0
)0

,
3,3

9,3

COOR

4,0

=J

COOR

74

3,0

COOH

C6H5x

20

16,0

11,0

CN

)=<

IV

125

,
(IV. 23)

--. 3 /,
/ = - 35,1OR11V + 56,65
(IV. 23)
,
. ,

-. R^,
P^ 3 /. (IV. 24). 3
/ = 12,47 P^-0,71
(IV.24)
- , - HCC
.
: 3 /= 7,12P^n, 1,18

0,132

(IV. 25)

. IV. 24.
R^v (, [11]).
/ ;
V ;
Vl "-5,6--1,3;
VII ;
VIU ; IX ; X ; XI :; XII
[4.3.1.0 1 -6] -2,4.

, (
. 1.3), , i
-.

. - 0, !
rpawc- 130. i
. IV. 23 , 3 / >

//;, <

,
.
*
. !
, ;
. |
3 , ,
2.2.2. R^. Ha . IV. 24
-
<|
R^v,
.
>
0,

/ = - 32,62/?^ + 48,45
: 3J = 21,91P^- 3,85
/ = _ 36,74/?^ + 60,68

(IV. 26)
(IV. 27)
(IV. 28)

2.2.3. HCC.
3 /
{- .
0, , . . IV. 12,
IV. 12.
-
3J 0 6'

0,5-1,5

2,5-3,7

;
:

8,8-11,0

4,0.

9-12,6

7,5

5,1 - 7,0

..

10,3

126

IV

3

J4Uc . ,
. ,
3
0 6' /-
.
2.2.4. . HH
,
. AE = E(X)
E ( H ) , X,
3 /
3
/ = 9,41-0,8OAE
(IV. 29)
:
= 19,0- 3,3
(IV. 30)
/. = 11,7-4,7
(IV. 31)
. IV. 13 .
(IV. 30) (IV. 31)
, X HH. 4--1,3- (46). , , 46.
CsC6 466.
, $Cd .
3JCd 3 / &, 466. ,
IV. 13.
- 3 / ()

32 Li
-SiR3
-CN

-Cl
-OCH2CH3

8,9
8,0
7,6
7,2
7,0

-OR2

4,7

'^

"\
N

/"

19,3

23,9

NiR 3

14,6

20,4

44

10,0

16,8

7,3

14,6

4,7

12,8

C=CX
/
Ni
CH3

Nl
44

"

127

300
360
180
2
. IV. 25. -
3/
( [12]).


, Hd. - , - 2 - (49).
,
3
/ 47 48.
/ --- 4 OAc

IV

128
1

1 I

IV. 14, - VHH () -

8,5

H3 , H

g
"

Q-X

>

8,0

J--Fe(CO)3

0
SI Br P\

?I

7,5

129

H J

Si

S
.

>.Mg

6.5

I t I I

[ I I

. IV. 26. - V2, (Ka, [13]).

-^
- -'
. Kapn-jj
, !
. IV. 25, ,
,
3
/ (, = 240, 0 = 120).
. , -;
,
;
3
/, . (IV. 29).
3
/
. -|
|
|
. ( ,
, |
|
, .) , ]
/ . cool
!
. |
/2,

3. IV. 26. / :

J HC
,
H
C-H, , , CH-
-CpX, .
(IV. 32), /:
3
J = 7,63 + 0,51 - 0,10
(IV. 32)
5

X.

130

IV

131




. 3 /
2
3 ,
, .
, . IV.14. ,
.
2.3. 4 -
( /, 57)
- 520

. ,
. , .
0,2 .
, - . ,
-
0,13,0 . ,
2
3
, J .

- - - . , -
/()
/(), - - .
- , -, . II. 12.
-. CH 5 2 -
(. IV. 27, ).
- 2 2 - , . . , :
, ;
- -]
-1
, 2 2 - .|

. IV. 27. - - .

. , ,
H
,

(. IV. 27, ). ,
.

,
.
, - - .
, . - - . . IV. 27, . , - 3 /()
(H) ,

=H. , /() -
10% . - ,
. , -
-
. , .
, , - -

5*

IV

, - .

.
,
, , (57, 58).

132

2.3.1. . - VHH 5 / , H

CH3

H^C^ V

-CH3

4/ M- W-.
, -, 50, H0, H 6 - 1,1 .
51 52
, - ,
-. 4
- -
, -
- .
, , [2,1,1 ] (53) [1,1,1] (54). ,
,
, - , ,
, .
H4

Br

133

C6H5
J =2,3
55

= 1,25
56

~ 1,5
57

W - 1,0

58

2.3.2. . , -, CT-, - - / .
/()
(IV. 33)
(IV. 35). /()
.
HC=CH:

HC=C-CH:

V () (H) (H)
5

/()(H)- (H)

HC-C=C-CH: () (H) (C-H)

(IV. 33)
(IV. 34)
(IV. 35)

H
- = 0,9

J = 6,7 -8,1

52

51

() HC=CH 6
, (H)=65-
2
6
(H) = 150 cos -10 . , ',

53

10

18

54

5 .]
55 56.
, 4J 6/ ]

- - <j> = 0 </" =
2
^= 180, = 90 270 cos
11
- .
5961 4 ,
, ,

IV

134

. IV. 28. -

( [101).
360

, 270.
5961 -
4/ . ,
4
/() . , 62, V, =
= 0 = 180. , =
= 90 ,
. 2.3.1, , 4 /() .
, 63 V
+0,5 +1,0 . - '
(64).
H.

HC=CCH
, . IV. 28. 4Juuc, =
= 90 -.
5 / , HCC=CCH,
4 /. , 5J ()
(. IV. 35), G- - 5 / .

5J, 1,4- (65),
. 0,69 .

-0,5-1,0

~0,8

= 0,S, NH
66

67

^^^
H
'.3O .

mpa/, *

""

68

H'
.

59
H

62

135


4
/() V () -

- , ,
-,
(. . 2.3.1).
- H4 H8, H2 H7 (66)

(67). ^J, -1,3
5J4Uc, - (68).
, - -
(69),
5 /(0). ,
- -

137

IV

IV. 15. -

. IV. 15 ,
, , .

13

-2,93
W3C-C=C-W
+2,7
W3C-C = C-CW3
+2,2
W-C=C-C=C-W
W3C-C = C-C = C-W
-1.27
W3C-C=C-C=C-CW3
+1,3
W3C-C=C-C=C-CE=C-CW2OH +0,4

3,0
(W 3 C) 2 C = C ;=cw 2
-5,8
H3C-CW = C = CHC'\
W3C-CH = C = CHC:i +2,4

C=CH 2

4,58

H 'H

-. ,
. IV. 29. , . IV. 15,
- -
. . , . ,
CH 3 (C = C)*H
, -
, , .
15Q -10

2.4. -

-
,
. , (. 3, . I). - . , AS:
AS = (3 cos 2 9 - 1) - 3 (/4) (IV. 36) B0
,
,
6 ,
, .
(IV. 36) , , , .
0 , . 3 cos2 6 1 , , AB =
C H 2 C l - CH 2 Cl

+150

+150 10

9OK

- 6 5 ' 10

+150 10

-10

-5

+5

+ 10

. IV. 29. - -^
. ^
(. . 2.3.2).
i

. IV. 30. H 1,2- 29,5


(I [14]).
- , , 37,5 , 1 0.170 HM ( ) "';, -! . '1 ,

.''2 ( ) ,

138

IV

139

'

20

30

40

J50

60

J.
70

_L

80

90

. IV. 32. 6--1--1.

. IV. 31. 2,3- 60 .

= ]
. , , !
-1
BO , -|
.
. ,
(. IV. 30). -:

(IV. 36) , . ,
,
.
, , -
, .
, -
.
0Ac

, . , 70 - H 6 1,1 . - ,
7

- .
- ls- . ,
, -
,
(. .).
2-5. -

- ,
, . XI. 2 (. ).

IV

140

IV. 5. . IV. 31 2,3-. - . ,


. ?
IV. 6. 6--1--1 . IV. 32. -
. , -, - . .
IV. 7. , 7-,
(71 716). 7- , /2. ^ .

141

IV. 10. : 76
77. 2,8 .
?
H

,0

76

77

715

71

? ,
/, ?
IV. 8. 72 73
. H0 13,1 6,6 .
?

1. Ham N. S., Mole T. . 74, . 4.


2. Bremser W., Dissertation, Cologne, 1968.
3. Paulsen H., Todt ., Chem. ., 100, 3385 (1967); Paulsen H., Todt K
Ripperger H., Chem. ., 101, 3365 (1968).
4. Pople J. A., Untch K. G,, J. Am. Chem. Soc., 88, 4811 (1966).
5. DeMare G. R., Martin J S., J. Am. Chem. Soc., 88, 5033 (1966).
6. Friederich H. F., Z. Naturforsch., 2Ob, 1021 (1965).
7. 15.
8. 7.
9. Pascual C., Meier L, Simon W., HeIv. Chim. Acta, 48, 164 (1969).
10. Sternhell S., Quart. Rev., 23, 236 (1969).
11. Pawliczek I. B , Gunther H., Tetrahedron, 26, 1755 (1970).
12. Pachler K. G. R., Tetrahedron, 27, 187 (1971).
13. Castellano S., Sun C., J. Am Chem. Soc., 88, 4741 (1966).
14. Gutowsky H. S., Kistiakowsky G. B., Pake G. E., Pur cell E. M., J Chem
Phys, 17, 972 (1949).

OAc

AcO

: , 4, 7, 14, 53.

72

73

IV. 9. 1--4-/7- 74 75 1,01,3 0,60,7


. . ?

/-

74

75

) Sternhell S., Correlation of Interproton Spin, Spin Coupling Constants with


Structure, Quart Rev., 23, 236 (1959).
) Bothner-By A. A., Geminal and V i c i n a l Proton-Proton Coupling Constants in
Organic Compounds. 72, T. 1.
) Cookson R. C., Crabb T. A., Frankel J. J., Hudec /., Geminal Coupling Constants in Methylene Groups, Tetrahedron, Supl. No. 7, 355 (1966).
f) Sternhell S., Long-Range 1 H- 1 H Spin, Spin Coupling in Nuclear Magnetic
Resonance Spectroscopy, Rev. Pure Appl. Chem., 14, 15 (1964).
) Barfield M., Chaktabarti ., Long-range Proton Spin, Spin Coupling, Chem.
Rev., 69, 757 (1969).
<0 Hilton /., Sutcliffe L. H., The Through-space Mechanism in Spin-Spin Coupling. . 74, T. 10.
*) Kovalewski /., Calculation of Nuclear Spin-Spin Coupling Constants. CM
74, T. 11.
* .
.

143

. II ,
- ,
. , ,

. ,
,
. -, ;
. , ! .
, , : - ?
,
. : ,
-
? , ,
, .

1.
.
, V1- ( 1)/2 - //. , - -
. ;
. , , A3,
A 3 B 2 .
.

A 3 X 2 , .
, , , 1,1- (. 2.3.1 . II)
1,2-, .
AA 7 XX' '' .

.
V. 1. .

H
J,

CH3

Cl

H 3 C-CSC-H

H 3 C-CH-OR

H 3 C-CH 2 -SH

CHO
C=C

CH3

2.

;

. ,
, , , , , ,
,
. , ,
1
ITo ,

144

145

, ,
. , ( ), , ,

, ,
. , .
, , , .
, . , ,
S0, -
. ,
, 1F.
- fp<1
.
E4:

, ,
. ,
. ^ , , ( ), 1V.

, . ,
, d/dx. , , . ,
' -*- ^ .

.
(V. 3).
V :

,
, ^.
2.1.

,
1F
. ,

:
yg\y = EW

5 = ( /2/82) (2/2 + 2/2 + 2/2) + V


(V. 3)
,
(V. 3), , . -
, . IV, . ,
(V. 2).
, <j>, -

(V. 2)

.
T
. (V. 2)
,
,
. , E ,
.

- , ,
. , ,
, (.
.1, . 3) :
3% = (-h2/8n2mr2)(d2/d<j>2)
(V. 4)
,
-

-. , 1F = N sin ; (V. 2) !
(V. 4)
(- /2/822) (2/2) (N sin ?</>) = EN sin
(V. 5)

(H2/8n2mr2) N sin q$q2 = EN sin
(V. 6)

( 0 )
B0, <(1)
- . 2(0)
v/, <(1) - (1)
/,-/. , < (II. 10), -
(0>
, <2^ , . I.
E= [IzB0 .
(1.5) (1.10) ,
E = ViJz(I)*. h, , - , . , 1/ (V. 1) .
, , P
, .
.
(V. 10) ,
7 7.

:

146


E = (h2/2mL2)q2
(V. 7) J
L = 2 (L ).J
^ = O, 1, 2, . . . , -j
, ]
. *]
*() = 1F (2 + ). E0, EI, E2 . . , ;}
. IV. 1
-]
,
2

=1

(V.

N 1//, \ sm2qd=

s= . ,
/

T/smq, <7 = 0, 1, 2, 3

(V.9}

V. 2. (V. 2), (V. 3)


1P = ATsJn ,
,
K = O

3.


^
{'
.

"'= Z V,/!/ S I v

(V.

147

1 = (1/2)

/ = i ( l / 2 ) P

/,P= (1/2)

/>=-/(1/2)

^ = (1/2)
/ =-(1/2)

(V. 11)

/ Jx, 1 /. , (V. ) /
,
P + 1/2 1/2 . , /, . I, I2.
-

dv

dv = \ dv = O

(V.12)
(V. 126)

* B0, , -
, E .

148

, HH-J
- P -
.
4.

(V. 2), |
, (V. 11), -!
, (V. 12). -]
, , , --]
!
. -|
, -J
V,- - J !
.

, ^
, ,|
!
- , -1
. -1
-|
, , !
!
. -j
, ?
,
.
4.1.

$
. < = <5^(0),
(V. 2) (V. 11) , ?

),
v A / z (A)o(A) =
= +1/20 (A), VA (1/2) a (A) = +i/2 a (A), +,/2 = (1/2)
_i/ 2 = ( ' / 2 ) V A co-j
_/.. i/2 VA.

4.2.

149

, -
(/,/ = ).

, .
,
,
/ () m/ (E), , . 2.1 . II:
( I ) ^ 1 = O(A)O(B)
(2) Uj = O ( A ) P ( B )

= +1
= 0

(3) ^3 = P(A)O(B) , = 0
(4) & = P (A) P () / = - 1

.
<5# <5^ .
= +<; E =
= + EB. \,
, 5#a(A)a(B) =<^ A a(A)a(B) +<^ B a(A)a(B).
, a (B) <3^ A a(A)a(B).
5^() a (B), , <# () =' () 5^() =
= ():
() () = () () + () () =
= ( + ) () () = Ea () ()
, \
\ = \. (V. 2)
<f>i, <j>2, 4,

. , =

[v / () + V1,/; (B)] a (A) a (B) = ,a (A) ()


[(1/2) VA + (1/2) VB] () () =,()()
,=(1/2) (VA + VB)

,
/ () . 7 () ().

, = (-1/2) ( V A - '
2 = (1/2) (VA
4 = (-1/2) (V

150

g5

* - H
<U EC
H ES

^ _

_
-

^" ' ^

0:

CN

D. QJ

<

m 1

CQ
O
Cf
O
X

<;

< < < <

CQ CQ

? ?" ^

S-

O.

^-V

^-~

^J

^J

PQ CQ

^ ^

X-^.

<,<,<, <^

- N - K-

SSSS

->"

/1

CJJ

<3

"
S

CU

Ol1

QJ

? ? I

]
^

CC^<1^

lffl

-I-

OJ

H
U

i ^. ' ^
N

' '
I
-
' *^*

~~'

<

s?

?i
I

<
*

Cj

+
CQ

"-*

S
^

S-

Il

CQ

*"->

CQ

CQ

CQ

+
to

tO

^i
CJ

Il

G
S

02. 8 CQ.
CQ. CQ.

<"

J,

SSSS

i t &

S +

Z^ Q ^

->
<|

H
CQ

+
-H I

<

ICN

<

CO

cj

CO

T T T T

j>

">

*
+

CJ

-P

+
^

-1

I
'

_^

'

t?

J<

Cj

;?

J<

1^. _|^,

<
!X

X
X

S?

->

-.

^
-^** -If

4..
X
?

- CM

CO

CO [^*

X^

^,

-|rj.

? > ?

ST

CO

-7^
. +

-4*

fO

<

. (N

i^

+]
tj
1

Ol

-J

i
^-v

I1* |-

-
?
I
<

-
?
+
<

^ J]N J]^
- N -|N
I
I

I
"5"

CQ.

CQ.

C^
S

SD
.0

> J

Ii

CQ

EB
EC
4)
BJ
H

CQ

<f
^ ^

<

~>:

> ^

+!
i1

IcN

^ CQ
.

"-

CQ

i
T

CJ

.S

~- ICM
J

<;

i,

Jj S

-,'

+ -H

+ I < <

)
2

fj

CX>
CM

' ~;

>,
-

I
1

i
^

<

TTtT

t t t t
2 S SS S

P.

O.

- S 3S

CU

.J

S
U

CD
CM

"->

--V

CQ

O
O

.S

"->

CQ

.1i

CR
O
O.
OJ

<X>
N

.E

O
X
QJ
Q.
QJ
C

(N

|ssg

151

CQ.

I
I

CQ

t
-ii

.
CQ.

__

B
B

m
C
S

H
S

t/)

CQ.

-
CB

CD
C

S
O

T
I

CQ.
CQ.

X
<j

'

+
N~

CO"

5^

CQ.

CQ.

152

153

, .

E =

dv / J

do =

(V. 13)

A2

B2

(V. 13) (V. 2) ' . (V. 13) , .

4.3. , -
(/,; - )

"A

flo

>

. V. 1. AB - /AB = .
; .

, - , . V. 1.
, VA VB.
(3) -> (2) ,
, - ;
(/ = 1). J
, |
. . V. 1 () ;
AB - . !
. 4.3.2.]
V. 3. , -!
.

|
-|
(V. 2). , !
-|
, , pp. !
. , , ,!

4.3.1. A2 .
-
; (V. 10). ,
<j>\<f>i , . . .
,
(VA = VB)
A2. , A ( I ) (2), ( 1 ) (2) (1)(2) (2) (3). ,
(2) (3) .
. , , <\ </>4 (1) (4),
(1)(2) ( 2 ) ( 1 ) , ( 1 ) ( 2 ) ( 2 ) ( 1 ) ,
, .

(2) (3)? .
. </>2 <f>3, , , *

1 2, = 2 () + 3 ()
(. 14)
(V. 2), , (V. 13).
|3
. ,
" : ( 1 ) , (2), (3) . . . ().

154

, ,
, ,
,
. ,
, .
C2 C3
(V. 14),
: /% =
= /3 = . ,
, C2 C 3 . (V. 14) (V. 13) ,
([C2 () + C3 (Pa)] \ 3 \ [ 2 () + C3 (Pa)] )
() + C3 ()] | [C2 () + C 3 (Pa)] >
\ ( | | > +

155

(. . ) ,
, , .

22 <
=0
(V. 17)

/7 O


, .
,
2, 32, 22 3 (V. 17).
(V. 10),
H22 = ($\3\ ) = ( | ^?<> | ) + < | ^\ )
,

\ > + C3C2 | 30 | > + C3 (Pa | \ Pa)

\ ( | ) + C2C3 ( | Pa) + C3C2 < | ) + C3 (Pa | Pa)

, :
22 = ( | $ | )
23 = ( | ^ | )

<ap 1^' 1 MaP) = (CiP I // (l)/~(2) IaP) =


= / <ap I /,/, + lylu + TJ, I ap)' =
= / (<P I //, I aP) + (aP | f/, I ap) + (a? | IJ2 | ap))=

(V. 12) 32 = 2,
= (|22 + 2C2C3H23 + ^)/(2 + ) ~
= ujv. ,
C 2 C 3 . /2 =
= ( l / v ) [/2 (u/v)dv/dc2]. u/v ,
/2 = (l/v) (/2 /2) =

= / ( j<ap IPa) + |(ap I Pa) -|(ap |ap = - -J- /

, 22 = ( 1 A)/; 3 = ( 1 A)/.
:
23 = ( | \ Pa) = ( | (0) \ Pa) + ( | M^ \ )
( | ^<) | ) = ( | VA/Z (1) + V A /Z (2) I Pa) -

= I V( c l + 0D] (2222 + 2#23 - 22)


C2, de/dcz . ,
, , ;

(V. 15)
C2 (#22 - s) + C3H23 =
/3 ( 32 = 2)
232 + C3 (33 - ) =

(V. 16)

(V. 15) (V. 16), , C3. - ,

(ap 1 5() I pa) = (ap \tT (1) 7(2) | pa) =


= / ((P 1 7,7, I P) + (ap I // I pa) + ( 1 7/ | pa)) =

32 (1/2)/, . .
-(1/4)/ -6
(1/2)/
(1/2)/

(1/4)/-

=0

// TJx + / + //, .

156

MP

157

(V. 12), . (1Fl1F) = I, C2 + C 3 = I . , 2 = 3 =1//2,


4r2 = (l/V2)( a P + P0)- E3 C2 = -C3 , ,

,
= . , (2) (3) ,
C2 C3 (V. 14).

-v \j
(X.

. V. 2. A 2 - / > .
Q : .

[(1/4)/ ] 2 (1/4)/ 2 = 0
2 = +(1/4)/ 3 = (3/4)/.

, , , '
,
. ,
- 1
2 3,
= VA = VB
. 4.2). ,
,
2 3
E3. , >
A 2 , . V. 2.
Ei E 4 , V A + ( 1 / 4 ) / V A + (1/4)1
, !
( V . 2 ) , |
.
A 2
C2 C3 (V. 14). )
E2 (V. 15) (V. 16)
C2 ( 1/2)/ + 3 (1/2)/ = 0
2 (1/2)/ + 3 (-1/2)/ = 0
, C2 = C3.

4.3.2. .

= 1.
, . .
. A 2 . ,
M
Wm 1Fn. (V. 18), I x . (V. 18)

= OF

(V. 18)

A2,
1
1
. F2-^ Fi:

M* = <1 ( + ) \ I x ( I ) + Ix (2) | )2 =
2

= 1 (1 ( | >+1 ( | ) + } ( | ) + 1 < | >) =1


1

F3 -> Fi:

M 2 = (-JL ( - ) | Tx(I) + Ix (2) | )2 =


= 1(1 ( | ) + 1 ( | ) - 1 ( | ) - 1 ( | >)2=0.

1F4-^-1F2 1Fi-^1F3 1/2 .


, , E3, ,

, . . VA. , - .

, ,
, 5 Tx .
, Wi, W2 Wt
S s =-J-I,
Wz S = 1. ,
<3|<|''1> < 1 F 4 ]^IW 3 >
( (V. 18)) .
, .
5
,
-. , As = .
A 2
. V. 1 () V. 1 ( B ) . -\ . , -
(1/4)/
(3/4) J. ,
. ,
, , / = -)-! 1,
, 1.
*. / = ,
,
.
A 2 , ,
. , , . .
, .
, ,
.

158

V. 4. , . V. 1(A),
(V.18),
AB , - .

4.3.3. . A 2
, , .
, , A 2

;
C2 ( V. 1). Y 2 W3
. 1F2 V.I

, . . ,
1F3 . , ^F2 Ws,
:
- (
-I- (

) = -^( + )

.(-) = -~(-

C2 S, - '
s = -f-l S = 1, ,
: S1F2= (-J-I)1F?!
S1F3= (I)1Fs- ,
, Q R (. .]
, QRW = ^(51F) -J
<Wn\R\Wm> , Wn Wm ]
, -J
qn qm, . .
qn = qm.
1

A 2 , F3-HFi
1
F4-> 4^3 .
(. X I ) .

159

4.4. AB
(V. 18)
* N (, , . .)
/ N = 2/ -f- 1 (.
(1.2)). N 1
UIiIJX , , .

160

MP

, .
-, v<j6
/ .
A 2 (V. 17). V A = VB , H22,
W23 W33:
22 = 0/2) V 0 U - ( 1 / 4 ) ; H13= H32 = (1/2)7;
=-0/2) V 0 S-0/4)

161

J
J
J
!
J
]
J

|
Z=(vA+vB)/2

=0

(V. 19) I

,
E2 + (1/2) JE - (1/4) (v06)2 - (3/16) 2 =

E2, = - 0/4) 0/2) 2 + (v06)2
EI E^ (V. 2)
:
E1 = (1/2) (VA + VH) + (1/4) ; E, = - (1/2) (V A + V B ) + (1/4)

(V. 14). E2
(V. 15).
2
2
= (1/2) -^J' + (^^) .
C2 [(1/2) v06 -C] + C3 (1/2) =
, 2 9
v 0 6/2C = cos 29 /2 = sin 29. ,
C 2 ( I cos 29) -C 3 sin 29 =
c2 = c 3 s i n 2 9 / ( l cos 29)
2

sin 2 9 = 2 cos 9 sin 9 cos 2 9 = cos 9 j


sin 2 9 C2 C3 cos 9/sin 9, |
\-\-\ \ :!
C2 = cos 9 C3 = sin 9.
3 C2
sin 9 C3 = cos 9. ,
(2) (3)
1
F2 = cos 9 () + sin 9 ); 1F3 = sin 9 () + cos 9 ()

. V. 3. - | / | > .

,

(V. 18). , 1 F 2 -^Yi
2

M2 = < [cos 9 () + sin 9 ()] \7 () + /, () | ) =


= [(1/2) sin 9 + (1/2) cos 9]2 = (1/4) (1 + sin 29)

.
AB
. V. 1(). , (v,\4-vs)/2..
-
; (. 2.3.2
. II) .
,
. V. 1, ,
AI (f\)
A 2 (/ 2 ) BI (/3) B2 (/ 4 )
.
. V. 3 AB,
v06 = 15 = 12 .
V. 5.
. .
V. 6. , . V. 1 ( ) , AB v 0 6 = 20
1
= 15 .
V. 7. = 2 (|) +(<) + 4 (|3).
V. 8. AB , /i / 2 = } / = / /4.

) Vo6/7? ) , )

, ?
6

X.

162

4.5. AX

AB,
Vo8 /.
,
v06 - . ( l / 2 ) ( v 0 6 )
sin 2 9 .
sin 2 9 = 2 sin 9 cos 9, sin 9, cos 9 . , sin 2 9 + cos2 O = 1, sin 9 = 0,
cos 9 = 1.
, AX, :
(1)
(1/2) ( V A + V x ) + (1/4)/
(2)
(1/2) ( V A - V x ) - ( 1 / 4 ) /
(3) -(1/2) ( V A - V x ) - ( 1 / 4 ) /
(4) - ( 1 / 2 ) ( V A + V x ) + (1/4)/
, . V. 1 (), .
(V. 19) ,
,
23 32 :
2 2 -

163

, , . , vo6 ;> 7;
. 2.3.2 . II , . , ,
,
.
, v06 J.
(1/2)7, sin29 1. . V - I ( T ) ,
fi f^ , /2 /3
, . . ( V A + VB)/2, A2.
AB, 2-, . ^ ,
,
. ,
,
. . -

, i . .
4.6.

,
;

E2 = 22 = ( 1/2) v 0 6-( 1/4)7 3 = 33 = -(1/2) v 0 5-(1/4)7


(V. 15)
(V. 16) C 2 + \= 1 C 2 C3, 1 - <,
1F2 1 W3 . 1
1
F2 = " F3 = Pa.
, !
- AX-J

,

.
,
. . . .

,
, 1/2
. 2" , , .
6*

164

, , , m r ,
1/2.
= C2 () + C3 () + C4 ()
.
, ,

w = ct

d -, a ^ -

1. 2 = H32 ( = Hu1) .
2. .
( ) :

= (C1, C 2 . . .
02

W
,
(f>i
, . - (2) (3) : (cos Q,

sine) (Jj) (-sine, cose) (Jj).

(V. 20)
= O,+!

i=\
(V. 10)
, , . . . , Hkk Hi2, ..., ,
H.

#22

#23

#32

#33

#39

X l #44

, ( . 4.3.2) .
P2
(. . XI) < x F f ! |^| x F m > , m , .
3. E
Hkk , ,
- :
6^ = 0 k=l
. 2, .
,
.
.
, , .
4. Hkk
+1/2
1/2, . . . , . . .
.

<f>k
.

(V. 21)
Ki

#44

#1

I Hkl \ = , = 1 k = I

,
, / = 1. ,
,


(, --).
//
:

165

T J/ = +!, i / , = \, *'

166

MP

/ .
( I I . 10).
$i

, ,
.
.
.
, ,
H,

Wk I \ = = JI,U

i I

U = I, <pi [ / (, ), U =
(, papa).

, .
:
= 3/2

= 1/2

(1)

(2)
(3)
(4)

= -1/2

HU = UD
(V. 22)
D , . . , : Dkk =
= * Dki=^Dik = Q.
, , (V. 23), H . ,
, . . \, ..., (V. 14) ,
, (V. 23) :

= -3/2

(8)

(5)
(6)
(7)


= (1/2) (VA + VB + V 0 ) + (1/4) (/ + /AC + /BC)
22 = (1/2) (VA + V B - VG) + (1/4) (/ - /AC - /BC)

0" 1 HU = D
(V. 23)
, (2) (3) A 2
, (V. 22),

8 = - (1/2) (VA + VB + V 0 ) + (1/4) (/AB + /AC + /BC)


:
==

\2

34 = (1/2)/

VA = v, VB=O, VG=V, /AB=


/AC = /BC = / :

Q-V-IJ

23 = (1/2)/
24 = (1/2)/

1
/
-v-

-J

= /7[8 = U

\%= ...

v-y

167

S-7-

41 ^

1
/

\-

\ -

/'l

V-

,/2

Jl
3

"-

~4'

^TO .
, H. D , .
, (V. 1)
(V.18).
,
"ItTKO .

168

, - .
,
, .

169

HB

5. v,- ///

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

.

<

i B

. V. 4. 'H 1--3,6--2- 60 .

5.1. AB
- . -, 1--3,6--2-, . V. 4. -
2--5- (78), 1--1- (79), 2,5--1,6-[10] (80) (81). . V. 5
- />06.

HB
Br

Cl

78

Br4

Cl

0-CHAHB-C6I

H3C-HC

C=C
\
79

0--6!
8

81

. V.5. - //v06.
JIv0S, 1 : 3 (), 1 : 1 (), 5 : 3 () 5 : 1 ().

170

-
, . V. 1, , / fi/2 / 3 /4 , f \ /3 = h h =2 , = V/ 2 + (v06)2/2,
AB


.
(V. 2). ,
.

Vo

6 = V4C 2 - J2 = (2 - /) (2 + /) = V(/ 2 - /) (/1 ~ /4)

, . . ^1 f 4
f 2 /, Z, VA = Z ( l / 2 ) v o 6 VB = 2 -f+ (l/2)vo6. , , . V. 1,

171

5.2J. AB2 (A2B). 2 -


, , , 2,6- (82) 1,2,3- (83).

C5 (84, 85)
(86).
HB

H3C

P2 P,
AB.
2C = / 2 /4 = V-^2 + (vo$)2
PI P)P2Ps. PiP 2 /, P2P3 = vo6.
P\PzPz 26, .
V. 9, VA VB AB fi = 38,5, fz = 28,0, / = 20,5 / 4 = 10,0 . .

5.2.

,

. 4.6. = 1/2 =
= 1/2 .
(V. 2).
,
,
.

82

84

83

85

/COOR

COOR

86

2 - . V. 6.
( ) , f \ f 4 -. 2 -
/7 /8 , /5 f s .
,
- *. 3 X 3 , = 1 / 2 = 1/2.
, Vi Jij.
2 - , A2.
B 2 .
* ,
.

172

. V 7. ABz.
; .

. V. 6. AB2 ( )

60 .

- -,
AB 2 .
. V. 2 .
V. 2. AB 2

(1) 01
(2) 02
(3) 03

(4) 04
() 05
(6) 06

B2

( + PI)/2

+3/2
+1/2
+ 1/2
-1/2
-1/2
-3/2

P
P

PP
( + >0)7/2

(7) 07
(8) 08

( - )//2
(-I

+ 1/2
-1/2

i I
2

, , , -
(8) ->
-> (7). 7 </>8 , E1 E8 </>7 <f>s (V. 2).
: E1 = ( l / 2 ) v A (3/4)/ 8 =
= ( l / 2 ) v A (3/4)/; , VA. , 2 - -, - / . , :
- *
- *

(4) -> (3)
()-
(2)-*(1)
(6) -> (4)

(4) -> (2)

(5)->(2)

(6)-> (5)
(5) -> (3)


. V. 7.
,
1 </>6
,
(V. 2).
1
Y 2 F5 .

, :
H22 E

173

S2

H23

TJ

* ^ 33

(22 = <i<j>2\3@\<j>2>, H23 =


^= < -2 \\ 3 > . .) ,
2 -.

174

MP

175

(2) (5). , AB 2 ;
(. . X I ) .
AB 2
:
. V. 8. AB 2 2-.

V. 10. -, ,
VA, VB / .

/ = 6,0 . Vo6 : 14,0 (), 6,0 (), 1,0 (),


-8,0 ().

/ 9 .
, , --|3.
(. . V. 6 V. 10) *.

87,74 91,7495,00

99,00 /\
107,26110,00
102,74 103,26

- ,
2- /AB/VO^
, ,

/AB/v 0 6 (. . X I ) . . V. 8 ,
2 - 3 - 2 -.
(. 2 . I I I ) , .

5.2.2. .
AB 2 , , , . , ,
AB 2 .
.
B2 ,
/ *, ,
( ) 1 ( ), . . B2 (S),
(T) . , 1/2, (D) , ,
, 1. / * ,
-. /* = . ,
, Ai/ 2 Bo Ai/ 2 Bi, . AB 2 .
AB 2
, / (. V. 26).
Ai/ 2 B 0 ,
* , , ,
, .

176

: A (P)-> () 1F8-^1F7.
, . ,
;
1/2. ABn -,
-.
(VA, VB / ) -.

, , ,
.
, , . 166, , , . V. 2 V. 26,
. ,
,
.
.
H1,

V. 26. AB 2

H32H33

-/5=1

Hu H45
H5* H55

5 66 67
75 76 77

88

'

|/2 0

(1)
(2)
(3)
(4)
(5)
(6)

+3/2
+ 1/2
+ 1/2
-1/2
-1/2
-3/2

0+1/2

0+1/2

0-1/2

+1

(7)

(8)

+1/2

-1/2

+1

D /

1 2

Z)- /

S0

+1

I
0

+ /
LJ
0- 1/2

0-1/2

-1

1,2,4- (87), 2--4,6- (88), 2- (89) (90).


HB

^
1
,

JB-

J1 ,

/ ^
HB

89
23

55 56 57

1 / 2 ,

H22H23H21
H32 H33 H31
H42 H13 H41

177

90


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

Ig

5.2.3. ABX. ABX. ,


, ,
VA VB. ,
X ,
. , (VA, VB V K ) - (/AB, /AX / B X ) , -


. V. 3.

(V.24)

178

179

V. 3. ABX

VM

(1)

(2)
(3)
(4)
d)
(2)

(3)
(4)

mT

+1
+i
+i
-i

I
I
I*
\f

aa

mT
a
ft
a
ft
1

cos (aft) + sinff (ft a)


-sin0 (aft) + cos (fta)
L_^____

a
a
a
a

(5)
(6)
(7)

(5)
(6)

(7)

1
~2

~i

f
ft

(S)

+i

(8)

"

ft
ft
ft
ft

ft

ft

cosB (aft) + sine (fta)


sine (aft) +cos (ft a)

f
ft
ft

m/(X) /z(X). B , .
- ,
-, .
, - ABX
ab-, m, (X): +1/2
1/2. EI, E^ E5 Es
GCGCOC, , (V. 2),
E2, E3, E6 E1 .
m^

,
X

AB-
. V. 10. ABX V 0 S(AB) =5,0
/AX = 4,2 /BX = 1,8 . ( [I]).

afr- - . 2---.

- ,
. V. 9. X .
//() Jz (X) ,
- :
Am, (X) =0. VA Vx
VB Vx-

.
V. 9.

ABX.

, / = 8 ,


- 8 - -. , 1F4-^-Y5 1F6 -* ^, , . -
Vx (. V. 10).
, X n , , , m/(X) (X) [= ] / Z (X)] . 2 - ab-.

180

181

= 33,5 , / = 19,2 . (V. 25)


VA, VB, /AX /BX, ,
:
f

IWn f\i \3
fife

= 16,9
VA
VB = 33,0

VA = 23,6 / = 19,9
VB = 26,3
/ = 12,3

/ = 6,5
/ = 1,1
=19,2

0,0 5,5

19,2 /26,8\
24,7 28,9

46,0 48,1
-38

+3,8

. V. 11. - 4--3---2- (91);


60 [2].
-; - ( ); 60 .

ABX 3 ab-.
(ABX, 1 : 1 ; ABX 2 , 1 : 2 : 1 ; ABX 3 ,
1 :3:3:1).
X , ab- v*. B , -
v*a = VA + m/ (X) /AX = VA (1/2) /AX;
v*b = VB + m, (X) /BX = VB (1/2) /BX
(V. 25)
.
- -.
ab-
, . 5.1. .
. V. , - ABX H 1 , H 2 H 3 4-----2- (91).
2
, , Br H
19,2 , ,
91
/ i / 3 , fs IT, /2 ft
fe /8-
: ab- I
f\, /, /5 Ir, ab- II f 2 , f 4 , fe f 8 .
-
(. 5.1) : I) Va =
= 13,6 , V1", = 32,4 , / = 19,2 ; H ) v * a = 20,l , v*b =

=19,2

ABX.
.
-
. , -
, V K .
1
Vx (1/2) (/ + / ) . , / +
+ /BX. 1 F 5 -^Y 1 4^8 ->- 1F4;
-
VX = V x + (1/2) (/AX + /)

Vx = V x -(1/2)

/)

91
(. V. 11,6). ,
f 1 0 fis, 7,6 .

__

. V. 12. - 91 1 ()1
2 \

182

183

, . IV.
, / A B .
H 1 H 2 ,
3
H -. 3> /BX,
, H 1 = H 2 E= HB (. 2.2.1 . I V ) .
, / (. 2 1 2
. I V ) .
-
, (V. 25)
-
. -
. V. 1 / .
, / ,
, . AB 2 .
V. 12. ABX 2--4.6-. -, . V. 13.
43,29 / \ 47,75
45,21 45,78

50,29

54,03

56,52

. V. 13. 1 H 2--4,6-.

(. . 4.6 5.4). , - ;
1 2, ;
. V. 12. , - :
, - :
. , 2 .

/ 10 / X. f i 0 1,
f n

/ /
- , . V. 14. , / /BX. , - .
/ .
10,0 .

/ = [ - '25 CAX - ' /(/9 - /?,)


(V- 26) J
. -1
fg , (V. 26) |
.
*
V. 11. ABX 91 ]
f 9 , 25,2 , .
I^ , (V. 26).

1 |
1
3
H - H . ,
VA, VB . . K
,

PHC. V. 14. -.
-v06 (AB)= 10,0 , / = 5,0 , / = 6.0 ,
= 5,0 , / = 6,0 , /BX= -2,0 .

= 2,0 ; -V 0 6(AB) = 10,0 ,

184

185

JLJL I

I
..
| | | I |

I I

.
M

. V. 15. -
ABX (. ).

-
/ / , - ABX.
. V. 15. ab-- ,
. J
/ /BX . J
,ab- , - j

HX
I

HA

C6H5-C-C-He

10,0

. V. 17. ABX VA VB. ( [3]).

Br Br

-, -. : / 15,7 ; / ^ Jft\ = 7,7


46 (AB) : 56,7 (), 18,7 (), 5,0 () -0,6 ().
2--2-.

I
^WvyMf*A/i4W
. V. 16. - ABX 1,2--1
.; 60 .

. , , ,
, ,
/AX /BX , 14 -. , , ab-
-, . . 2 -. . V. 16
1,2--1- 60 . -
5 . , /
fz,
ab-.
(. V. 17)
, -

186

- ABX ,
.
-,
,
,
.
- ; , , ,
ABX; ,
(V. 24). ,
- - , .

AB-

-U' ^JL
0,0

6,2

9,9

16,2

187

V. 13. - L-ac, . V. 18.


20,4

30,8

ABC,
, . , ( )
. , .

5.3.
-12,6

-8,3

-1.9

1.9

. V. 18. -
100 AiTu). - .

*12.6

L-

VA V B . , AB, - . ;
/ , \.
. |
- - - |
X , , J
. |
, / = /BX, ,
. , -
- X.

, ,

m, S

= +2

(1)

(2)
(3)
(4)
(5)

(6)
(7)
(8)
(9)
(10)
(H)

(12)
(13)
(H)
(15)

(16) pppf

-
. '', ,

MP

, , ,
, .
, '' , ;
/- (92), (2) 1,2-*
(93).

X X X
X X X

S-*.

FX-

t=(

^
S

S
S

X
X^

--

^S
O

CU
3

OJ

<3

S
E-

S-

*^

CQ

S-

CQ

C-

- >- ->

E-

X X X

. *, -

C^
S

)
3
E

*^

*^

S
^,

CU
OJ

CX

t-

a
D.
f-

CU

S-S-O
+

^-U''

*' -^^

"^

ct

<

(N

S-

M
OJ

^"
^**

X
-

CJ

X
X
H

^D

CX

+ ? 7

+ +0 T T

--^

III

<

X X X
X X. X

X X X
X X _

OJ

E-

* |
, *""'
,
.

<

CU

T
0

* i

22, 8- -


X,
- : VA, VX,"
/'(=/), /'(=/), / ( = / ) /'(=- ''- OT
VA v x . : 10 '- 10 '-.
; , AA'- '- VA VX . ;
/ =/= J', X . , , (v06 = VA V X ) , . ,
/ = /', ;
2 .
1 : 2 : 1 .

'' - A 2 : s+i,
S 0 , s_i 0 (. . V. 1); -1
AA' XX'
''. -i
, -j
: #, = S+1 (') s+i (XX'); <f>2 = s 0 (AA')X S + 1 (XX')'
. . ]
*, ;
(') XX', -,
V. 2 '-. .|

S. SL S^

HA

V< '

^H

^-^

< < <

CJ

X
X^

T T T
&
S*-*.

189

188

"" T

190

MP

191

/77,

-1

-Qg)

-i

'

. V.19. ''.

'-,
(').
,
. - i
6 X 6 4 X 4 f
2 X 2 ; - !
1 X 1 :
.
-

ab \
; \Mempuvmt
j

!
ab-\

, "
(), }
A 2 AB, AA'- '-|
2 !

". V. 20. ''.


-,

Mt-?! ab- ( , d, e, I
' S, , I, /) .

<

t92

MP

*/ = < 5\\ ,>


<.1\@\>- Hki = Hik,
(1/4) -E
(1/2) L
__

V. 4. ''

T* (7) -vA + -K
(2)v x + T /C

(8)

v A -v x -y

l / f (9) -v x +-i-K

/1
C\
10

I J

193

(10) -VA-VX+!

/1

'

^ '

ab. 12 - 12 X, 8 ( ) ; , 20
( 10 ).
, . V. 19.
,
( V A + V x )/2, . . V. 20 '- ,
: / = 9 , Jx = 4 ,
/ = 8 ]' = 2 . , ; . V. 19. a, k b, I 2
. ab , d, , f g, h, i, I .
(v a , Vb / ) ,
'' (/., /, / /'). , V. 2.
5, ,
, ,
(V. 2). :
/ + / = , / - / = Al, / + /' = #, J-J' = L (V.27)
, . V. 4.
V. 14. , . V. 4.

(5) (6) (13) (14) .


. Hkk = <.\2$\5>
, <^\\^> <\3\>

-(1/2) L
_(/4)/- ^ 0
(1/4) (
M)

-(3/4) Af - -(1/2) L
=0
-(1/2) L
(1/4) M-E

(V 28)

'

(V.29)

. (5) (6)
(13) (14)
Et. 6 = - (1/4)/ (1/2) /2 + L2;
2
Ei3, H = - (1/4) M (1/2) V^ + L2

E2 E3 AB (. 4.4), , M
- ab
ab- v06 = L.
. V. 4 (1/4)(/( M)
13, ,
''; . V. 5.
, ''
.
, , AB A2;
:
M = a b = k l;
K =g h = i j
(V.30)
M = c-d = e-f;
L = V(A - ') (8 ~ l) = V(c - /) (d- e)
,
VA ( vx) = (1/2) ( + ) = (1/2) (k + /)
/ = (1/2) ( + M); / =-(1/2) ( -M); J -=(1/2) (N + L);
/' = (1/2) (N -L)
(V.31)
V. 15. '- '', . V. 21.
V. 16. . V. 22 '- ''
H1 H4 2-. ,
" , ''.
7

X.

194

V
V. 5. '-
''

(2)->(1)

(10) -(9)

(13) ^- (12)

(15) ->(14)

(14) ^- (12)

(15)->(13)

/ v . \

*i

__/
1

jM-VM

(5) -> (4)

(7) -> (6)

i
i
L.M + VM \
\
i

~~2

(6) -> (4)

(7) -> (5)

(3) -> (2)

(9) -> (8)

"^T

+ L2

27,98 3155

\/~ + L

yV/C->- + L*

/K2

44,50 48,45 52,02 .

38,55 41,02
38,98 41,45

^t / f '

35,50

\fW+T7

-jM-^]

'2 + Z-2

. V. 21. '- '

+L*

>- + L*

jK + ^^K'-

<iSK2

+ L2

1
N

'', , .
''
/ L, , M.
, , ab- , ]
. , ,
, , . , '' / /'.
, , . , VA VX,

7,4 7,7
1

10,6 11,4

14,1

. V. 22. H 2- (
).

196

b.l

t
\

. V. 23 '- -
' '

4-

60 ( . \4]).

, - / Jx, J /'
. , , ,
.
,
'', .
, , '' (
X)
, , , 2-.

'';
. 5.3.2.
''
, ,
'' ''.
- 92.
'- 4-,
. V. 23. ,
- , -

197

. / opro- (J) /-
(/'). , 2 -, 79 (. . II. 2),
1 2. L 57 , -. - ab- M
,
- (/ Jx) . M 1 ,
46 . ab- (g, h, i /)
3, 4, 5 6. ab- (d ). ( f) 2 ,
M .
, , , opro-
, .
X Y
, v06 , , - .
, ''-.
, XCH 2 CH 2 Y ''. . ( I = F i I I ) ,
CH2CH2
''.
NH

H?

II

, , :

198

. V. 24. '- - ''-


100 .

1. I ^t II H1 H*
H3 H4 , , , VI = V 3 = VA; V 2 =
= V 4 = vx.
2. / [3 = / / 24 = / ,

199


AX (. V. 24). M
. , , (M) / / ''
(. . II. 19, ). A 2 X 2
, / = /', . . L = O.
X.
, ,
, 1 : 2 : 1 .
. -,
ab (d, , h i)
, . -,
ab- . ft /.

(. V. 25).
''
, / / . ,
M ( M) ab- , AA'- '-

'

- ^ '

= (1/2) [/23 (D + /23 (H)] = (1/2) (JrpaHC

+ J }

J' = (1/2) (J12 (I) + /12 (H)] = (1/2) (/' + /) =

= (1/2) [/34 (I) + /34 (U)] = (1/2) (/ + /)

, '' .
, 10 . , /, L, M N
, M
!
/ > /', N > L.
ab-
h i, ; *

L- 1,0
M = 2,0

/V= 2,6

. V. 25. 1 H 60 ( . [4]) '-.

201

200

5,

1
X

Fe(CO) 3

. V. 26.
''-

[4.3.1.0''6]-2,4- ( [5]).

6 . [-!..'-'^ (. V. 26).

X , ''
''.
v 0 6(AB),
'' .
4- (. ) / 2,,
, . V. 20;
''. , ,
'', .]
:
, M
!
''. (',
;
V. 2 ,
. ;
'' . Mo:"
, , *

. V. 27. ''
V6(AB).
. V. 27. '' ; Vo6 = 30 ; s Vo6 = 20 ; Vo6 = 15,0 :
Vu610,0 ; V&6 5 .
J = W , = 1,5 , / = 7,5 / = 3,0 .

(3), (5), (6) (8)


- ,
, , (. . XI). ,
''.
''
, :
,
(v,\ -+-VB)/2, . , ''
, . , k / , 12 . . V. 27
'' ''; ,

202


- .
5.4. -
,
, ,
.
, -. , , ,
. ,
.
. V. 28
9,10--9,10-.
, . 4,
- ;
. ,
- .
, , , , .
- , .
, , , ,
.
. -,
, , -, -
, , . . .
, -

203

, COOR

245,41

. V. 28. () () - (60 )
9,10--9,10- (, [6]).

,
.

,

NMRIT/NMREN, ,
LAOCOON, -.
,
.
v /^.
, . .
, , . 4.4,
U .
,
, :
Ep-Eq = fp4
(V. 32)
Ep Eq , fpq
. ,

204

NMRIT/NMREN Ep. , (V.32) ,


(1)- . ,
,
.

vl1', /^1, , . U, v^Q|, JfL


V 1 / 1 , (', ,

U ( 1 ) v(.21, /^2.1.
-ro
, . V. 3.
LAOCOON . ,
,
[
; (V. 34)]:

(V. 33)

^1E1 = O

, ,

.
U,
H =
. UpqEq

fpq
cod~

Z (/ - /,)?

;-1

205

(V. 34)

k , a (f 3KC n /
i- . ,-
(V. 35)

\~

| U "*] \ Htte

2 Z (/ /,)/ (///) =

(V. 36)

, ,
(V. 37)

V.3

\JJJT J ^Pi ~

(V. 38)

, /, .
^ />

207

206

TjO
i

LJ

H*


<

&

, il

El , U0

fn/j :

(V. 37)

? , .

, .
.

.
*
1.
2.
3.
4.
5.
6.

4.
Carbisch E. W., Jr., J. Chem. Educ., 45, 410 (1968).
Schaefer ., Can. J. Chem., 40, 1678 (1962).
Grant D. M., Hirst R. ., Gutowsky H. S., J. Chem. Phys. 38, 470 (1963)
Bleck W. E., Dissertation, Cologne, 1969.
Gunther G., Hinrichs H.-H., Justus Liebigs Ann. Chem., 706, 1 (1967).


: , 34.

\59

Sop

V. 4
, .
Ap/. ( V. 4). LAOCOON, .
.
. ,
,
.
:
, -


) Dischler ., Systematik und Analyse von NMR-Spektren, Angew Chem 78.
653 (1966); Angew Chem. Int. Ed, 5, 623 (1968).
) Carlo P. L, Hirst R. C., Magnetic Resonance Spectra of Multispin Systems
J. Chem. Educ., 46, 345 (1969).
) AuIt A., Classification of Spin Systems in NMR Spectroscopy, J. Chem.
Educ., 47, 812 (1970).
r) Garbish E. W., Jr., Analysis of Complex NMR Spectra for the Organic Chemistry, J. Chem. Educ., 45, 311, 402, 480 (1968).
) DIeM P., Harris R. K., Jones R. G., Sub-Spectral Analysis. . 76, T. 3.
) Jones R. G., Use of Symmetry in Nuclear Magnetic Resonance. . 76, T. L
) Bishop E. O., The Interpretation of High-Resolution Nuclear Magnetic Resonance Spectra. . 73, T. 1.
) Hoffman R. A., Forsen S., Gestblom B., Analysis of NMR Spectra. . 76,
T. 5.
) Diehl P., Kellerhals H., Lustig E., Computer Assistance in the Analysis of
High-Resolution NMR Spectra. SM. 76, T. 6.
1
) Gunther H., H-NMR Spektren vom AA'XX' und AA'BB'-Typ Analyse und
Systematik, Angew. Chemie, 84, 907 (1972), Angew. Chemie, Int. Ed. 11
861 (1972).
* .
.

VI

- (102)
- (103) ,
AB,
A2. 104 105.

,
, , .
, , ,
, , ,

, , . ,
, .

1.

,
-,
. 9497 CsH6O
H

H H

1OZ

103

209

H H

, , ,
.

,

,
. , - 106 '', - - 107 108 AB 2 M A 4 .

CH3
94

96

95

97

97,
,
2 : 1 ,
. 99101 ,
H

98

99

H3C

1OO

16

17

18

, ,
, 109111,
A 4 , ABC 2 '' H

Cl

Cl

Cl

1Ol


,
.

113

VI

210

.
, 1 1 2 A3 AB 2 .
. (114118) A 4 , , .
H
H
H
Cl
Cl

115

114

116

H
117

118

(119123)
, ,
.

(124 125) ,
. VI. 1, , 124
ABC, HH ,
125 '' A 2 -

124
VI. 1. : ) 1,3-; ) <--1,2- ; ) --1,2- ; ) 1,4-;
) 2-; ) 4-?
Vl. 2.
.
VI. 3. 1,6;8,13--[]-[14]
''. , ?

119

122

211

123

, ,
, ,
, .

,
.
A 2 , AB, AB 2 ABX,
,
,
.
, -
. , .

212

VI

(. VI. 2)
AB 2 AB. (15,5 10,0 ) AB -
C3-C4 ,
, , , AB 2 . 7,34
C 7 ,
65,12 ,
. -
. 1,63 1,57, .
2,0
,
-;
. :
.
Cs, . -

213

LT)

. m

(Nt

irf
OO

"

"

8,0

7,5

7,0

8,5

8,0

7,5

. VI. 1. H (60 ) 1,5- () 1,4- () .1


. VI. 2. |
(60 )
(. )
-! (
. [I]).

LO
Ol
~

215

VI

214

CM

. VI. 4.
[2]).

5.6

5.8

6,0

6,2

A 3

2 1

OS

(60 ) 3,6-

(,

3,6- (. VI. 4), .


2.

7,4

7,

7,2

7,1

7,0

6,9

6,8

. VI. 3. (60 ) () - ().

. VI. 3
. ABC-, --j

''. !

,
.
<
, !
- , *

66
.

,
, , D- -
,
, .
. , , D-
L-. , (126) Z)-I H? .
1,6 2,5 60 100 . , , -
.

C6H5-C-H,

126

127

128

216

VI

217


IMi

<5
. VI. 5. (60 )
- (5)-3,3--2 ( - ;
[3]).
.

- ;
, - ;
, - ^
(+JSOL ()SOL - '.
o-X/(+)SOL L-X/(+)SOL I
D-X/()SOL L-X/()SOL [ - \
(SOL) - |
D 1 L-X], . Be- |
, ,
,
, , . ,
/- (128)
0,14 . ., 20 0C 30 % ( ) (+)- ()-1- . 40 0C .;
0,47 . . , ,
, ^
-;
.
,
.

, ,
, . . VI. 5
. 3,3--2 4- - , (97%)
S-.
: (+)(-|-) ()(+), n-
. , ,
, . -
. , . , , .

. .
-CH 3

CeH 5 .

6,00

6 5

/C-C 6 H 5

OCH 2 CH 3

5,80

5,60

I 1 AO

20

. VI. 6. (60 ) 130,

218

, .

L- (129) 60,90 0,83
.

CH3

CH 2

HjC-C-O-CH 2 CH3

CH2-CH3
H3C

H
4

CH -*C -COOH

C6H5

I ,.

.P-C6H5
'

130

131

(130) , 3 - (.
VI. 6). , ,
(131), .
,

a H
. I I
b-C-C-R
I I
H

IIII .
, H1 H2 . , ,
, H 1 H2 , vi (I) =?=== V 2 (III), V 2 ( I ) ===== Vi (II) V 2 (II) v, (III)
- R. R
,

X
133

-S-O-CH 2 -CH 3

-C6H5
6-CH 2 -CHj

129

2ia

VI

1335

H.

H.

134

. VI. 7. (60 ) .

(. . 2.3 ). ,
, , , 4--2,6,7-[2.2.2]-2,6,7- (132). 2- 1
, 0,04 . . (
).
(2,3 60 ; 3,6 90 )
, , .
, . ,
() CH 2 R-rpynnoft,
, , , , . VI. 7.
, ,
CX 2 R ,
, X
, . ,
,
. --X
X

VI

2.20

(133). X ,
C2 C2
CX 2 , X
(1336). A 2 2,7--1,6-[10] (134).
CX 2 R . , 2--1,6-[10] (135) AB.

C6H5

JrC

136

2--1,6-[10] (136) , . , ,
, ,
.

LJ[J

^^/
135

O\J

.
. 6 , . , :

V l . 4. ,
.

0,N

,C5
CH1

8
H
H

(
~0

221

3,

VI

223

( ) , () ().
, ,

AB ,
2, CiC2C3
C2. ,
. VI. 8, .
3.
13C D-

0,0 5

. VI. 8. () () |
( [4]).


,
,
104 . (. VI. 9),
.
13- .
1,1 % -13 .
1000 989
12CHCl3 11 13CHCl3. -13 / = 1/2, -
13C , . -

"V H

. VI. 9. 'H , -
.

.
VI. 10.
1 13C
H - 1,2-.

225

Vi

224

/( 1 ; i CHM) .

/(A 1 M). 12C , , VQ. *

(. VI. 11) . /( 1 3 )
, ,
, ; /( 1 3 ) / , 199 12,5 . - 1,2-
/ , =
= 5,3 . , 13 -,
- .
13C - . , 1,4- 13C
''-,
''.
.

c
H1H

t t

t t
. VI. 11.
13C; R .

H -1,2- |
|

209 . B-J
13- 13CHCl313.
I
C ]
-
, 12
-, (.
. V ) . 1,2- (. ).
A 2
3
/ . ^
13
, C, *
AMX, X = 13C,
13
13
/( C-): /( C-HM). :
:
13
V A = V 0 + (1/2)/( CHA)
UM
13
,Cl VM = V + (1/2)/( 1 3 CH1) J m, ( C) =
0
13
v'
=vo-(l/2)/(
CH A ) )

13
\
1 (
VM = V 0 (1/2) / ( ] )

13

C
- (. VI. 10); , /( 13 C- )

Vl. 5.
.

13

C -

CHCt 7 - 1 2 CH 7 Cl'

H
15

12

CH2Cl- CH2CL

'3,
H3C-CH2-CH3


, 13C , - 13CH,
*
.
X.

226

VI

227

. VI. 12.

1H 1,3,5 ()
7--1,3,5- (); | 2 / , | =
= 2,0 , (VI. 1) | 2 / , | =
= 13,0 .

) Jacobus ]., Raban M., An NMR Determination of Optical Purity, J Chem


Educ., 46, 351 (1969).
) Raban M., Mislow K., Modern Metods of the Determination of Optical Purity. In: N. L. Allinger and K. L. Eliel. (Eds.), Topics in Stereochemistry,
vol. 2, Interscience, N. Y., 1969
) Gorkotn M. M., Hall G. E., E q u i v a l e n c e of Nuclei in High-Resolution Nuclear
Magnetic Resonance Spectroscopy, Quart. Rev., 22, 14 (1968).
r) Jennings W. B., Chemical S h i f t Nonequivalence in Prochiral Groups, Chem.
Rev., 75, 307 (1975).

13C A 2 X A 3 X - A 2 A3.

.
- HD JH,
/. = 6,5144/,

(VI. 1)

. VI. 12, -1,3,5;


. ,
. ,
1
H 29
Si, 1
29
- H, Si.
6,8 .
. 3 . VIII.
*
1.
2.
3.
4.

Cardillo G., Merimie L., Mondelli R., Tetrahedron, 24, 497 (1968).
Grlmine W., Redecker K., personal communication.
Raban M., Mislow /C, . .
4.
. .

8*

. II

VII


Il

/.,


. 1 .
, . , -, .
,
-. -
. , , .

. VII. 1.
;
Bi
; ' .

1.

/ = 1/2 . I. 2;
( ) ( ) z- ,
B0.
(i.
B0 ,
.
;
(. V I I . 1 , ) * . , ,
WQ = Y-Bo ( COQ z-). ,
V 0 = (/2) B0.
,
* , B0
.

229

BI
(I, . ,
Sj KX, ^-
, ,
. .
C(x,y,z)
'(',',')
(. VII. 1,s). B ' B0,
' = 0 + <>

(VII. 1)

' CO/Y
Bf,
'. BI , ,
= 0 , ' . , , ,

' .
\,

230

. U

VII

. VII. 3.
2S1 : Bi(O B i ( r ) .

. V I l . 2.

Bi.

', S0, , (VII. 1),


= ^' + B1 = B0 + / + B1 = B0(I- /0) + B1

(VII. 2)

6 (. VII. 2, ), ,

I-Cou

(ViI. )

B0 ^ BI B 0 , ,
:
1) MO , , ,
(VII. 3), I g B , . .
6 180 < COQ > ( B 0 ^ B ) ) .
2) , am ~ to, TO tg 0
9 = 90. B 1 , LI
Co1 BI, . .
' (. VII. 2, ). , LI
. B 0 ^B 1 , , (2),
,
. , , ,
.
\ -.
Bx, -.
. *, -.!
, 2B 1 M

. V I I . 4. M LI; ,
.


B I ( / ) BI (),
.
(. VII. 3).
2.

.
, . . .
B0

.

\ > N0, .
M M0, ,

VII. 5.

"oil .

232

. II

VU

233

. V I I . 6. M '
.

(. VII.4). ,
, , .
, ,
,
2B 1 , . ( = COQ)
B 1 ,
M .\
{
> ' (. VII. 5, ). -j
M ^
, B1 ,
. ,
M z (. VII. 5, )

,
.
, >
, <
,
, .
CUQ , M :
(. VII. 6). Ec.
1
Mx (
) = coo a
Mx-
My' (. VII. 7).
90, !
, ,
,
dMx/dt dMy/dt. B !
.
*
, ,

. VII. 7. Mx,^
ACD M , ,
.., M ,.

.
(. XI),
.

', :
-M0^B1T2
_
,
~~

T2^

,^ ,

,2n2 T r

(ViI. 4J

Mx'
My Mx .
, , 0 ,
B1, M0
TI 7'2 (
. 3). , , ,
. VII. 7.


. , .. I,
(Ls) (LE) . . VII. 8
.
,
/ . . III, ,

234

. II

VII

235

.
, ,
, . ,
.
, 2
19
, H F ( ). 4
"
.

. VII. 8.

, .
, .

, .
- , 1 H ,
. , ,
, ,

.
. , ,
1 , 0,015 % 60 ,
.
, .
1 10~8 .


, .
( ). , , , -

3.
,
:
z ,.
, . .
.
3.1.
M0
B0 \,
2-
.
dMJcIt = (M0 - M2)IT1
(VII. 5)
1/T1 , , .
, . , (VII. 5),
, \ - .
, . 2. ,
|1
180 z B1 , z
. , z ,
( I. 1 1 ) .

. Ai 2

236

VII

. 11

X'

. V I I . 9. B I ; d .

. V I I . 10.

.
-,

. III. 6, . ~ ' ;
, .

!/-.

B1. (VII. 4) ,
S1 /
( = O)0)
/ ((B0) = COnStIB1T1

(VII. 6)

T1 , , , . . . . VII. 7
. VII. 9
B1.
Mx, ,
'. , , dMx/dl,
, . , ,
. , .
,
Af M /
(VII. 7)
Af = AAv AvA^ 1/(2) Av =
==1/(2/) . , , 1/
I/\. \
, ,

237

, -
0,1 .

?
-
;
,
(. . 3, . I). , . . ,
, .
Bx' By', COQ,
. ,
, . ,
.
, \ ,

. ,
, 103 . \
1O-1 , .
(. VII. 10).
, (. VII. 1). T1 ,
(1,1 % 13 C),
- .
, .
/ > 1 / 2
Q.
, . , ,
V I I . 1. TI
()
, 20 0C
CS2 (11 .%, )

19,9
60,0
2,7

238

VIl

, ,
, .
1 4 N 2 H , . 1 4 N
(Q = 2-10^ 2 )* ( ), 2 H , (Q = 2,77-10~ 3 ).
3.2.

,
,, , (/-. T2', ,
Mx, . T2 -
,
(. ).
T2
. , 0,1 .
0,1 ,
.
T2, \,
.
T2 = T1;
, !/- M0 z-.
z-- I
, T2 < T 1 . - , Mx, ,
. Bx' (/) By-(t), ,
M2, Mx,
Bx' (/), Bz- Bz ; , -
.

.
B - IQ- 2 8 2 , .

. II

239

. VIl. 11. ()
() .

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

. ,
Mx, , ,
. , ,
- , M, . Mx, (. VII. 1 1 ) . ,
B0 (. ).
, , , Mx, , BO-
Mx, , . VII. 11.
, .

VII

240

II

241

- ,
= 2/75,

(JJ

. VII. 12.
( ).
,
, . > , BO (T- . )) .

(. . III. 6).
.
, M
z-, M B1. M BI
. MO , . ,
Mx,
.
, (. 2),
.
t, t \ T2. , M
.

( VIII. 4) BI, ..
Y 2 Bi^ 1 T 2 < 1,
2
/() = const -B1T2I[I +( 0 -<fl) 7l]
(VII. 8)
( = W 0 ) :
/ ((O0) = const B1T2
BI , :
/1/2 = const ( 1/2) T2
1\/2
(VII. 8),

Cu 0 - 1 / 2 =1/7 2 = 2/2
(VII.9).

(. VII. 12). MXiV -

1/ = 0 /2+1/ 2

(VII. 10)

. Tz (), =1/75. (VII. 8) , .


,
.
, , , , ( ),
. ,
,
- T2, ( VII. 9),
. ,
,
.
4.
- ,
BI (
1 ). BI ( 10400 ).

. , , ( ) -( )-.
- M 2- , /-,
. VII. 5, . , - , ,
T2. , (), . V I I . 13.
, , M
(. VII. 5, )

(VII. 11)

242

(JMP. Il

VII

M
S

..

\.
/^

'

' ^- ,.

/^

^X

.-

243

,I

"

. V I I . 14.
Ti
.

( ) , (),
z (), .
. V I l . 13. U, - |
,,, .
I
TI, T 0 T 2 ( 180- ).
'$
TI iz
i
90- , M
(y/2n)Bi , , , tp - |
.
, , . - |
180,
. .
= 90, T 0 ,
, .

. ; = 180,
M z. - |
T0 = TI In 2 = 0,6937!
(VII. 12)


\. , \
(. 3, . 1). -,
CH3

, 90-
180- () .

, TI T2.
4.1. \
1\
( . . X). ,
(\/\) -13. ,|
\\ )
.
M (. VII. 14, a).J
180- , -J
, M () - M -!

V l I . 15. .

VII

244

M0 Mz , (VII. 5)
In (M0 - M2) = In 2M0 - /,
(VII. 13)

1 H . V I I . 15. 180, 1, 90, () 0,1 50 .
T0 , 2,25 . \ 3 .
TI .
4.2.
, . VII. 16.
M, z . , ^'- , ,
. 90- M -;
' ( ) . -
BO
( ) .
180-
, ' (). , ;
' ( ) . !
.)
, -]
90, , 180.
, -1
-
, . . !
M

. V I I . IG. ()

. Il

245

2,
. , - (2/ 2 ).
, ,
.
, 180-
, , 5
. . ( ).
, 2, 4, 6 . .,
( t / T z ) , ,
.
4.3. -
, -
M . ,

. , .
,
, -
,
, , .

- , ,
v, Av. , - - VQ, . . V 0 tp, \/tp, \/tr, ir
.
. VII. 17,
.
, , , BI v/,

246

VII
. Il

A(t)\

C(f)\

tr

/\ IiI

1 III i i i
I

>

IAp ,

HlTrK

.^*.

<

'tr

"
. V I I . 17.

- Vo,
t\ .

,

. {|

-, (VII. 2), |

2

I 9 I = (2/) [(v - v,) + /2) ]'/

(VII,!

\, (/2) BI:,
> Av, (v v<), 5

^ "1

(VII. J

Av
BI. 90- |
(yBitp = /2) (/2) BI |
,
< 1/(4JtAv)
(VIM
, *
, .

247

,
. VII. 17, ,
, , tp tr . , ip
tr. B tp Av
.
, ,
Bi. t, ,
,
() .

?
. ,
500 10 0,5 .
,
250 500 . , 2 % , , . , .
, , , , ,
.
, , . - .
, .

, . I, ,
, , , .
,

"
- , , ^ ,
. V I I . 13. , T'; ,





Av,;.-
IWOM^UIT
~~~---

1
\'(i v/

VII

248

Il

249

f ( t ) . ( ),
F(V).

: .

,
( ).
:

+ 00

(VII. 17)

(VII. 18)
( / = l). f(t)-*~F(v)

(VII. 19)
ft-O

76,9

V0

. VII. 18. ,
(); 6
.

. ,
, , Av;
( V o ) , Tl
. , , (/-

(. VII. 18), 1 .
, ,
. VII. 18,
.
( ), :

F1- /- , Tk k- , N . (VII. 19)


, .
, .

, ,
. VII. 13, , . . VII. 19, . -
.
( 1 ), , , ,

250

VII

II

251

*
1. Technical Bulletin, Varian Associates, Palo Alto, Calif.

: , 5, 13, 23, 45, 49.



) Marshall A. G. Comisarow M. ., Fourier Transform Methods in Spectro
scopv, J. Chem. Educ., 52, 638b (1975).
O) Smith W B Proulx T. W., Pulse-NMR An Old Analytical Technique Often
Neqlccted by the Chemist, J. Chem. Educ., 53, 700 (1976).
.
.

900
. V I l . 19. - 0,1 %- [1].
; ,
1000 ; - 1000 1 .

. , ,
, / (. VII. 19). -

(, 13C 1 5 N); -. , ,
,

.
. IX ,
.

253

VIII
-102'

,
.
,
.
, ,
.

1.

N.N-. N
,

/ ~\
3

\H
HC
3

. ,
, ;
;
VA VB. N j
+* '. -'
,.?

-114

(
88 /, 21 /). - - , (. . 3 ). ,
12O 0 C
. ,
- -.

2- (137).
,
(. V I I I . 1). 2- 2- (+),

/
N-C

'

-123"

. VIII. 1. 1 H 2-
(137) ( 0 C).

(V 8 )H 3 C

-116

137

254

MP

VIII

,
41 .
,
1 .

-65

t6v(l/2)n

-10

255

+ 37

. VIII. 2. 1H (0C).

. .
30 / (7 /),
.,
, , , ;
.
,((
|
!
(. V I I I . 2). -650C !
, AX 3 . , ||
- , -~|
^
. 37 0C !
, - -1
; , -|
CH3 . -|
, *!
.

(VIII. 1)

6v = / va vb
. ,
, .
(VIII. I) ,
.
2- 2-.
. - . OCH3,
(+3/2, +1/2, 1/2, 3/2),
.
-
( V I I L l ) .

. .
, .
,
,
,
.
, .
,
. ,
10 ~' 119,7 /
(28,6 /), 100
60 , , 4,2-10^ 7 / (10^7 /).

256

VItI

1.1.

257

dv

, , , ,
.
, v
TY , . 3.2
. VII, ,
T2.
,
va =*= v&, ,
va v&.

-;
- :
, /.
, feAAfA, - /=
. -?
. (. . IX)
g(v) -^
:
3
2
2
g (v) = [(I + ) P + QR]/(4n*P -f Q )
(VIII. 2)f
2

P= (0,25 -'+0,25 6v ) + /4; Q = [-v - 0,5(pA-J


-)6]; R = 0,5( pe)6v v(l + 2); = /(
+ TB); , TB
; , PB |
; 6V = VA VB ;"*
() ;
() (--),
AA AB; v
(). , TB ^

. VIII. 3 (VlU-,;
. 6v "

. VIII. 3. =*
.

= 30 , PA = PB = 0,5 A = I 1 O
g(v). VA VB.
.
,

, (VA + v B )/2. POM P
9

X.

258

VIII


PA PB
.
1.2.
(VIII. 2) ,
,

.
,
, 10~' 105 ."1. 20 100
/ (5 25 /) . , ,
.
, . 2
, . ,
- . , , . . , *
. , .

,
,
, ,
, (VIII. 3), . ,
. - ,
, !

(VIII. 2) , .
(VIII. 2). . ,
. V I I I . 3.

259

. ,
, Sv , . .
. ,
,

(VIII. 2). . ,
, ( V I I I . 5). . ,
.
, ^ AS^,
(VIII. 6) (VIII. 7) :

In k = - EJRT + InA

(VIII. 5)

logA
(VIII. 6)
')-!]

(VIII. 7)

(), R (8,31 /), kB


(1,3805 -23 /), /
(6,6256 X
34
XlQ- -), , 1.
(VIII. 8) :
(VIII. 8)
1* /, a

-~'--'.
:
(VIII. 9)

AG* = 19.14 [10,32 log (k/T)]

log (//)= 10,32 -( /19, 147 ) + (AS*/19, H)

(VIII. 9)
1

(VIII. 96)

\og(k/T) 1/,
^/19,14 10,32-) AS^/19,14.

9*

260

VIII

; = 1 -
, (VIII. 6)
(VIII. 7), , , , .
, .
-:
In = - kG/RT = - '/ + 5/

(VIII. 10)


. , . .
,

. , .
, ,
,
.
T2 , .

,
.
,
. , -
.
.
1.3.

(VIII.2) ,
, . :
(VIII. 11), S
PA = PB^
2,226v

(VIII. )

261



. ,
* = 1 9, 147- (9, 97 + log T1K011 V6v) ( /)
(VIII. 12)
(VIII. 1 1 ) , VA
VB , k/8v > 2,22. ,
k/8v < 2,22, (VA +
+ VB) /2. ,
, , ,
(AG^ ^
-T 1 AS*).
,
AG^ , . , , . ,
.
k , ,
.
, , ,
.

, , - ,

:
= - -
(VIII. 13)

, (VIII. 2).
( ):
!/ = & =
( ):
A0611

(VIII. 14)
(VIII. 15)

(VIII. 14) (VIII. 15) , , ,


, . ,
,

262

VIII

. ,
, , .
, 6v
.

, .

6v .
, ,
. , ,
6v , , . Sv
k .
,
.
, , , ,
, k .
.
, , ,
. , , ,
, ,
. - , .
,

.

2 / (0,5 /),
.
,
. .

263

1956 1969 .
, ,
29 12 / (7 + 3 /) 118 8
/
(28,2 2 /). .
(10
60 ), - .
, ,
85,8 + 0,8 / (20,5 + 0,2 /) (5 + S ) - I O 1 2 .

1.4.
, (VIII. 2) ,
VA VB. , , , .
,

?= +=

A x=fc B ^=fc C

, , AB
A2. (VIII. 2) , - .

. 2; ,
, .

,
. .
.
1.5.

,

.

VlU

264

265

, -> . [A]/[B] ,
,
[] []. . VIII. 4
138 1,2- 139. , 4,8 3,7, H0, &
139.
62,4, 138, .

138

, 80 0C.
7O0C.
[138]/[139] .
k (8O0C) = 6-10~5 ~'
,
(VIII. 9)
115,4 / (27,6 /).
2.

8
1

. VlII. 4. H (138-^139) -ds.


;
80 .

nocjie

,
. , .
, .

(E3, ^, AS^ AG^), ,
.

266

VlU

2.1.
2.1.1. . ,
D D N ,
A
/Q
D-C^

, , N CH3
,
.
H

0,N

D-N^

D , , -, , . , , , ,
( ) ,
. . V I I I . J ,
.
AB A 2 . ,
--2,4,6- (140),
- . 14Oa
V I I I . 1. / ( /)

55,9(13,6)
H3C

H3C

OC 2 H 5

-,/?
/

H3C

^Gf70 68,9(IE1O)

^TjC x
H3C

U
H

\3/

'\ H

Ea

9 (2Z

H3C

H3C

\.

> CH3

4^33,0(7,9)

>>(
^

H3C

50,2(!2,O)
Ea. 4,0(11,0)

4 H*

62,3 (14,9)

\
\\

Ea ~ 42 (W)

267

NO2

/ N\CH

14

,

AB, , , , . AB
A 2 (. V I I I . 5).
, , . 1.4, ( V I I I . 2), ,
, . ,
. 4.2 . V, , , pp.
( 1 ) ( 2 ) ( 1 ) ( 2 ) . ' PCX
,
. , " - .

. . , .
,
. VIII. 5. / = V( V A ~ v n) 2 +6 7 W V 2
,

.
2.1.2. . , - .
,
, .

268

,
-50,7

UJiS

VU^^X

,
0,AOO

4w-52,

0,180

-50,2

0,110

120

-39,5

0,026

-3A,6

O1OIA

-32,7

- 26.3

0,005

+36,2

10

-5

a
. V I I I . 5. () () --2,4,6-
( . [I]).


'.
.
H

269

VUt

H
H
H

H
,'

. VIII. 6
. ,

180

240

300

,
. VIII. 6. -
.

,
12 / (3,0 /). .
, ,
,
.
, . ,
(. 2.2.1 . IV).
.
19F,
. X.
,
- ,
. , -
-, -
2 : !.
141, .
(-1260C) 31,/ (7,4 /).

270

271

VIII

, ,

(32,6 /) - (. . 2.3.1 . II).

,
2,0, . CH2 AB. , :

(C6H5-CH2I2N-CH3
H

3 T CH3

(C 6 H 5 -CH 2 I 2 N-CH 3

4-

141

142

(C 6 H 5 -CH 2 I 2 N-CH 3
H

142
2 : 1 .
- (. . X). 134 0 C , 77,4 / (18,5 /).
2.2.
,
,
. , ,
,
. .
(143):
H.

C6H5-CW2
N-CH3

143

,

. . IV
143
AB,
. . -

(C 6 H 5 -CH 2 I 2 N-CH 3 +

, ,
, ,
. ,
, .
, -
NH N-
( = 2,0) ,
.
,
.
k', ,
k' = &[]/([] + []). , .

. , k' . & = (2 I ) - I O 5 ~', AG^ 42 / (10 /).
155 0 C.

. , ''- - (144) 108 5. 81 / (19,4 /).
- (145) , ,
(> 180 "C), . ,
, , 7--7-[4.1.0]-

272

(146) 146 1466.


Cl
Cl

t-

146

, , 2,3-[2.2.1]-5 (147), . 14Ta^ 1476 0| = 60,7 / (14,5 /).

^AA

I
?

AA

16 ,

5,7
'

-39 0 C

CH3

CH3

147 a

JY AA

'

,CH3

CH3
57 0 C

1L

C2H5

145

273

VIIF

,H

IH IH

1475

Ha . VIII. 7 , , 570C,

, 390C. ,
5-,
57 0C .
AB (61,7
62,1), , (~62,5), (~S4,0)
(6 6,5) .
, - .
(148)
96 / (23 /). , ,
, ,
, ,
N .
, 3
(s/? -> sp2) -

__/

AAJl

I
8

. VIII. 7.
[2.2.1]-5 (147) (, [2]).

H 2,3--

. , 149 ! 49,8 / (11,9 /).


2-
-NO 2
4

CH2-CH3

149
148
,

.
150152 (R = Cl CH3)
'

C)O-C3H7
150

151

152

153

274

VIII

,
R = COOR . ,
N, z
2
sp sp ,
.
,
. ,
(153) 4O0C , 7O0C
''. .

275

-9

2.3.
-j
!

-^
.
|
.
AH^ = 42,5 0,4 /&
(10,8 0,1 /) AS^ = 11,71 2,1 Kr1
(2,8 0,5 -Kr 1 -- 1 ).
()
- (, )
(). "
, . VIII. 8.
-
E
- . |
, !
, .
. VIII. 9.
( [3]).

OL

Of-'

. V I I I . 8. ,

H -dn

. -*-'
1/2, , ',
. , ka0 kae

- ! 2 , kaar.


~ ' (. . 1.3 . IV).

-dn,

VItI

276

5 3,80

_L

. VIII. 10. .
0

100 Cl
0
[4]; -15O C
(-1
0
, [5]); -15O C [5].

-
. Pe
. VIII. 9 (
. IX). !
1
. . VIII. 2 !
,
-8O0C.

,

(. VIII. 10, a).
V I I I . 2.

CN
F
I
Br
Cl
OCD3
SCD 3
CH3
C2H5
-?
C(CHs) 3

0,24
0,276
0,468
0,476
0,528
0,547

1,07
1,7
1,8
2,1
5


.
0
C

-79
-86
-80
-81
-81
-82
-79

2,10
3,39
3,48
3,99
4,23
16,1

277

HOi-Tb ,
, AG 0 = RT In . ,
jKeiuie. B . V I I I . 2
, . ,
(F 0,135 HM; Cl 0,180 HM;
Br 0,195 HM; I 0,215 HM).

. OCD3 SCD3,
, .
,
-15O0C
.
.
(. VIII. 10,6) (. VIII. 10, ) , . .
, , . ,
:

H
H

^
2>6 / (5,4 /). ,
(25 /, 6 /), ,

. 15O0C ^ ,


:
H

278

10

VlII

(4 + 2) --,
6 3,0 ,
, 6 9,3 .
4O 0 C, . 8 5,4 , 10O0C, , ,
8 5,29. - , . [18]
,
. , [18] , . -
,
( 3O 0 C),
,
.

[16] . 3O0C
6,74.

-13O0C : 1) [16]
( ) , ; 6O0C K= (/) =2,9: 2)

5 5 - 1

i
O

279

i
-2

. VIII. 11. [18] (3


. [6]).



. . V I I I . 11
- [18] . , ]
6O0C,

, , 0
JJ .
, 8,
,
.
,
, , ' " - .

VlU

280

2.4.

281

+!2O C

,
,
,
.
3,4-
.
,
C3 C 4 Ci Ce
[3,3]- (. +).

\
\

.'


, HOSTOIJ

, * '
. |
,


. , ,
?
. , !
2 5, . '

,
.
,

, !
. * ' BJ
, 7
1, 3, 4 6 ^

3O0C,

neper
'
(154). *
. '

. VIII. 12. (
. [7]).

8O0C,

(. VIII. 12). , -8O0C
154.

. , ,

49 / (11,8 /).

- , (155)

282

VIII

-!59 0 C

H(159)

3,0

. VIII. 13. ,
(158)^(159) (, [8]).
.


(156).
.
|
155. 7- (157).

154

155

156

157

|
(158). . VIII. ',
. -

5,72 (158, / = 9,5 ) 2,86 (158

. 3,74 8 3,50
- -
(159), 63,64
(158). KOJ
.
COOCH3

COOCH3

'COOCH3

158

159

283

, ,
.

-TOIiOB . ,
159 673 + 21 / (161
4- 5 /) , 158,
1
1
(2,85 0,03 "1 --') ,
11,9 0,1 -Kr - 158. ,
,
, : AG^s = 2,88 /
(0,69 /). 29,4 0,6 /
(7,02 0,15 /) ' 9 0 ' 2 159- 158.

16

161

(161) .
7,1 / (1,7 /) ,
42 -'-- 1 (10 K - ' --') .
160^161 38,0 / (9,1 /)
30,1 / (7,2 /) .

( -),
[16]. , , .
OT, !-()2.3,4,5,6,7-.
(, , , )

(, , )
^Pyr :
1) ** * ;
2) a ^ = ;
3) + ^ .
350C 6
Jj HHO
^ 5,80 5,76, ! , , .

284

285

VlU

-65

CH3

/--

,
!
0,05 .. !
,
.
41 0 C. ,

, /

.

, a =* =


,
, , '
6v * + . E


, , (VIII. I
<5v k
, .
0
AG=^ 2 C '
61,5 / (14,7 /)
71,5 / (17,1 /)
. , H.
,
162, 163,
, 163 Jt-;
8 / (2 /) '

. V I I I . 14.
1,6;8,13---()[14] ( . [91).
AB ,
C2/J. -1380C
-, , ; .

, 162 . , 163 .

a
162

163

, 1,6;8,13-6
Uc()[14] (164). ,

(4 -f 2)--,

- . ,

286

VUl

, . , 164
. ,
- , CeC8 Q 3 Ci 4 ,
. . , 0
. IV. 14 138 C,
. ,
- .
,
7 14 .
164^
^164 -'
.

. V I I I . 14
.
30 / (7,1 /),
10 1 2 ' 2 . , , , 165, ,
:

6,2 2,5 1 : 4, 4.
:

164

165

CH2=CH-CH2- -MgBr
166

BrMgCH2-CH=CH2
1666

3,3- (167),
, . 530C '', 320C
A 2 X 2 (. V I I I . 15).
,
168. '' CH3

mpem -Bu

H3C-C-CH2-CH2-MgCl
CH3
MgCl

167

168

. A 2 X 2 , L (. . V) . X
- . ', X X' , . . . (169+* 170), .

, 48
8 / (11 2 /).
'

1645

, , pea*
.
2.5.

^
^
. ,

287


" , 1[
. , Fe(CO) 4

288
-53 0 C

289

Vltt
-260C

+ 6O C

. VIII. 16. 1 H
(-, [Ul).

172 , 173
.

. V I I l . 15. 1H 3,3-<|
: '- ( . [1O]).

(171)
(. VIII. 16). 60 0C *
1 : 1 : 2 , 1

^
JCH3 . ,
*
-^

\
Fe(CO)|
/
H3C
.
FefCOl4
,
171
^
.
]
. ,
(172) N-!
(173)
33 / (8 /)
65,5 / (15,5 /) . *

172
Fe(CO) 3
<

^~
4

N-COOR

173

H3C

CH

174


. , -. . (174)
(. VIII. 17).
(/ = 2,1 )
CH.

10 X.

VItI

290

291

2,1

()

2,1

. V I I I . 17. 1H |
- |
- f
(, - [12]). I
CH3

. , -1
(VIII. 4) !
- , -1
- |
174 (/1,5 6,8 ; / 4 ,5 3,5 ; / 2 , 5 = 1 /,5= "
= ):
J
/ = (/1, 5 "T /4, 5 ~ 2/2, 5)/

'{-.


105 55 0C
55,7 3,3 /
(13,3
0,8 /).

.

1,2- (175), -
(176). , ,
.
H3C

CH3

5,0

(i ^'^'])^ '

"

3,0

1,0 8

(177) , "dMmiecKoro . 178


^ SbF 5 SO2F2.

..
3^^
CH3

175
177

178

179

292

VIII

. VIII. 18. -
4 : 1 : 6 ,
, ,
|

(. .
VIII. 1) 2,6- , ,
1, 2 6, |
5 7 .
, .
C30.
113 0 C 2,3- !
45,2 i,
2,5 / (10,8 /),
^
(100 + 3 0 C ) .
|
SbFsJf
SOClF SO2F2, |

293

158 0C.
. ,
, 4 -
. , (. V I I I . 18), (179),. . .
C2 C6 ,
. 177, ,

,
. (VIII. 2) ,
24,7 + 0,8 / (5,9 + 0,2 /).
, .
180, , 181. -! 3
CH3

CH3

'CH 2 -CH-CH 2

18

181

CH 2 -CH-CH 2

CH3

VIlLl

CH3

63,35 62,16. . 1050C , , ,


8 = 78,2 / (18,7 /).
, 182
,

294

VIII

OAc

295

H 3 C-C-CH 2 -C-CH 3

OAc

AcO
OAc

fr

182

. J, I JII 1 1 . 1 .

3.

12

, , . , . , ,
.
. . VIII. 3
,
.
.
V I I I . 3.
( - | ~'),

H2O
H2O2
CH3OH
CH3OH
RS+H2
RSR3N+H
R3N+H
R 2 NH
(3)3+
H 5 C 6 C=CH

+ H3O+
+ H3O

+ *
+ H3O+

=t=i

k2

H3O+
+

=* H3O2
=<=i CH3OH*
=> CH3O+H2

+ RSH

=:
:<=>

RSH
RSH

+ H2O

x=fc

RsN

+ RSH

+ R3N
+ OH+ (CHs)3P

+ ~

+ H2O
+ H2O
+ H2O
+ H2O
+ RS+H2
+ RS+ H3O+
+ R3N+H
+ H2O

=*= R 3 N
=?=fc R 2 N+ (CHa)3P+H
=* (3)3
*= H 5 C 6 -C=C" + H2O

10'
2 - 107
3
s
10
2
10
6-5

-2

10
5-10
102
5 - 102

" "

IO

IL

. V I I I . 19. H
.

- , -, .
. (. VIII. 19) [6(CH3)
2,2; 6(CH 2 ) 3,7] [6(CH 3 ) 2,0; ( = ) 5,7],


(&<10- 1 ). , ,
.
,
. ,
86 % 14 % .
.
,
, ,CH
HC
.
"Al"
Al
H C^
'CH '
. . VIII. 20
183

TO
0
. 55 C ,
183. .
3

296

VIII

162

297

149 ,

Cd(CHj) 2 .

91 0 C

J(115Cd1H)

. VIII. 20. 1H - ;
(, [14]).
\

-1
;

/ CH3
3

Al

/CH3

Al

/H 3

Al
H3C^

Al
CW3

CH 3

\ '
Al
3

.3%

Al
CH3''


63,5 / (15,6 /).
, -;
;
,
.

-
,
,
:
, 1 1 1 Cd (13%) 113Cd (12%)
, 1/2,
1 1 2 Cd . :
,
- !

. VIII. 21.
1H (, [H]);
( . [15]).

(. V I I I . 21).
, ,
.
, ,
. , 13C ;
Cd-,
, , .
4. 14N


, 1 4 N.
(. 4 . I), 14N 1, , (.

298

VIU

. 3.1 . VII).
, 14
N . , N H

m, ( 1 4 N ) = I , 1
1 : 1 : 1 .
,
,
.
, 14N
,
.
1 H, 14 N, 1 H
( 1 4 N- 1 H, 14N-CH).
- 1 H 14 N, . , 14N .
( 1 4 NH 4 )+ 1 : 1 : 1
(. II. 9). - ,
,
.
, - 1H1H , ,
14
N,
. . , 14 N. .
14
N , 14N 15N,
1/2. , , .
,
NH
. ,
. 1.3 . I, . ,
, ,
(. . 1 ),
14
- N1
1
1
- H H- H.
, H2O,
+
- HsO . -

299

.
, .
- N H.
*
1. Heidberg /., Weil J. A., Janusonis G. A., Anderson J. . J Chem Phvs 41,
1033 (1964).
2. Anderson J. E., Lehn J. M., J. Chem. Am. Soc., 89, 81 (1967).
3. Bovey F. A., Nuclear Magnetic Resonance Spectroscopy, Academic Press,
New York, 1969.
4. Japan Electron Optics Lab. News, No. 4 (1970),
5. Jensen F. R., Bushweller C. H., J. Am. Chem. Soc., 91, 3223 (1969).
6. Sondheimer F. et al, In: Aromaticity, The Chemical Society, London 1967.
7. Schroder G., Oth J. F., Merenyi R., Angew. Chem., 77, 774, (1965)
8. Gorlitz M., Gunther H., Tetrahedron, 24, 4467 (1969).
9. Vogel E., Haberland U., Gunther H., Angew. Chem., 82, 510 (1970).
10. Whitesides G. M., Witanowski M., Roberts J., J. Am. Chem Soc 87 2854
(1965).
1 1 . Ben-Soshan R., Pettit R. J. Am. Chem. Soc., 89, 2231 (1967).
12. Mackor E. L., McLean C., Pure Appl. Chem., 8, 393 (1964).
13. Olah G. A., White A. M., J. Am. Chem. Soc., 91, 3957 (1969).
14. Ham N. S., Mole T., In: J. W. Emsley, J. Feeney and L. H. Sutcliffe (Editors), Progress in Nuclear Magnetic Resonance Spectroscopy, Pergamon
Press, Oxford, Vol. 4. . 74.
!5. Bremser W., Winokur M., Roberts J. D., J. Am. Chem. Soc., 92, 1080 (1970).

:

39.


) Johnson C. S., Jr., Chemical Rate Processes and Magnetic Resonance. In:
J. S. Waugh (Editor), Advances in Magnetic Resonance, Academic Press
New York, Vol. 1, 1965.
) Binsch G., The Study of Intramolecular Rate Processes by Dynamic Nuclear
Magnetic Resonance. In: N. L. Allinger and E. L. Eliel (Editdra), topics in
Stereochemistry, Vol. 3, Interscience, New York, 1968.
) Kessler H., Nachweis gehinderter Rotationen und Inversjonen diirch NMRSpectroscopie, Angew. Chem., 82, 237(1970); Angew. Ohern. Iftt. Ed 9,
219 (1970).
r) Lehn J. M., Nitrogen Inversion, Fortschr. Chem. Forsch., 15, 311 (1970).
) Lambert J. B., Pyramidal Atomic Inversion. In: N. L. Allinger and E. L. Eliel
(Editors), Topics in Stereochemistry, Vol. 6, Interscience, N^w York, 1971.
Johnson C. S., Jr., Moreland C. G., The Calculation of NMR Spectra for Many-Site Exchange Problems, J. Chem. Educ., 50, 477 (1973).
) Handloser C. S., Chakrabarty M. R., Mosher M. W., Experimental Determination of Values by Use of NMR Chemical Shifts, J. Chem. Educ., 50, 510
(1973).
) Krahnbuehl D. ., Metzger P. M., Thompsen D. W., Fay R. C., NMR Studies
of Stereochemistry and Npn,-Rigidity df Titanium-p-Diketonate Complexes.
J. Chem. Educ., 54, 119 (1977).
* .
.

301

IX



, ,
(
1 H 1 3 C), , , . ,
.
.
-, , ,
, .
,
, , , ,
. . X
. ,
, , .
, , . , .

1.

(. V) ,

, . |
( - -|
), , -3
, -|
7/vo8 . , !
- -"
, -)

. ,
. , B0 ^i

. IX. 1. [I].
, ; . . . (. V I I . 8)
( ) . / ;
2 ; 3 ; 4 ; 5 S.

, ( I. ).
, .

50-
1,0 T 40 1 H. 60 * (B0 =1,4 T), 60-
100 2,3 T.
,
.
,
. , , , Hf
ie 4 , . . . .
* - , .

302

125

115

105

95

85

30

20

10

. IX. 2. 220 ( [2]).


. IX. 1. S, .
, . .
,
, ,
,
B0, 4,7 T,
200 1H. :
;
'1
, 9,7 T, . . -;
400 1 H.
:
, ;
B0, |
5,1 /220 (. IX. 2) *
, 1,4 /60 (. VI. 3)|
ABC, '
60 , 220
AMX,
.

. 1
(VIII. 11), k :

303


6v
. Sv, ,
,
, . . .
Q
CH3
184. S=O
, ,
H
\
, 15O 0 C
C-CW 3
CH3
250 (. IX. 3).

184
( ), 6v.

, , , ,
,
, . , ,
20
60

100

. IX. 3. 184 -15O 0 C ( . [3]).


" ~~- ; .

304

IX

305

.
(, ,
), ,

. ,
.
, , ,

[ 2/3 (III. 3)] 6v ? , 4/3, B0.
2.
-

BI. ,
BI B2.

B2.
2.1. -
B2
, , 2 = 2jtv2,
:
'= I ( v , - V 2 ) T 2 ( O +
i

+ Z Z V ( O / ( / ) - Z (Y/2n), B2/, (

(IX. 1)

(V. 10) j-x B2.


Z (\/2) B2Ix (O B2
, , -,
. -1
, |
B1.

. IX. 4. X AX VA V2
A2 B2 .
2 ; B2 .

,
(IX. 1) . ,
AX. V 2 -
(/2)2 > 2/ ,
X
. . IX. 4
Fe(CO) 3
AX - [1,2--()185
(185)]. X VAV 2 . VAV 2 = O, X . , ,
: .
. ,

306

IX

C-

807

COOC 2 H 6

Jl,

Il
V

V2 (&)

V2

I
t

.,

"

,1

I
I

. IX. 5. ,
.
; ;
.

,
-
(. I V ) .
,
-,
. VII. , V 2 , , = B2, . . | B2 ,
, '. , |
.
/ ( X ) / ( A ) Z H X ' . ,
, . . - ,
, (II. 6).

.
B2 , -

O S

. IX. 6. .
; VJ = VCH

;
, S1 (. IX.5,). ,
, .
, Ss.

,
.
, Av
S1.
, Av .
,

, Av.
,
(. I X . 5 , ) .

308

. IX. 5,
V 2 VI. B
. . IX. 7 .
V 2 VI, , .
. ( /-2- )

, , HB,
(. IX. 6, ). B2, AB
(. IX. 6,6).
186
(. IX. 7). , ,
. 66,7 (. IX. 7, ). H 7 H 8 .
63,81 4,61,

20

. IX. 8.
H 1 1 H 12 187 (
. [5]).
; Va = V (!, H 5 ); , ,
V 2 = V (H', ">).

7,5

7,0

. IX. 7. 186
(. [4]).

309

&
U

H 6 H6. 4,28
1
H ; ,
, .
(. IX.7, )
8 4,3 ABX H2H4,
.
.
- . ,
H4. H2 H3 ,
- .
, 62 = 6,28; 63 6,39 4 = 6,14 . .
,

. ,

310

IX

,
. ,
-
OTHOCI
, .
. 1
.
1,6-[10]
(187, . IX. 8) H 1 1
H 1 2 AB,
,
-
V H2 H5, H
H 10 .
]
H2 H5 -:
, H7 H 10
- . ,
H 1 1
, ,
W- - lJaHn
, 4 / .

, ,
-
. , -1
- AX, - , ^
,
2 - B 2
VA VX,
Hx. , , , ,
B2 , , ,
:

VA = VA +

Y2Bf

at V A '

8n (v A -v x )

311

,
V 2 = Vx +

42 (V A -v x )

(IX. 3)

VA Vx.
Av' = v. \{2.2. -

B2
. B2 ( , B2 ,
) . B2 -

"

''

(IX. 21

<
V A V A
1
V 2 = Vx '
VA V x ^ / A X . "

1
Uc. IX. 9. - AB 2--5- (, [6]).

IX

312

. ,
,
. AB fi /3
/4, J2 .
(. IX. 9).

- * , \ E3 : . J
4 -> \. , - |

. , - |
(, f 2 f 3 ),
, I
- |
(, /2, [4 fi, f 3 ). I
|
-
: & = 2. Am 7 - = .

313

/t\1

/' I \

aa/3

a/3a

/3ac

X 2 4A

ctpp

//

A4

M4

/
cra/

X3

M,

A,

a/3a

\pact

!V Vi
M,
I

X| A 2

yftp

X4

A3 I

pap

A4

M3

X2

PPP

. IX. 10, a.
AMX V A > V M > V X I / |>
| ' |>| '| + + + ( I) +-; ( II) - .

2,3- (188). AMX,



, . IX. 10, .


I
I

Br-CCOOR
I
I
Hx Br
188

'1

, |
( ), |

(. IX. 9). ,
-
J
. -'
OTHO-]
- B j
, .
* tickling, ,;
.
,


12 I (. . IX. 10, ),
, - , VA >
"> VM > Vx /AM > / > /AX > . / () / / ,
.
I , MI M2, M3 M4,
X 1 X3, X 2 X 4 . . IX. 10, ,
/ 12.
B2 AI,
, I, M3 X 2 . . 7 10
, MI Xi . .
5 9 . , II,

315

314

IX

-
'' ''. , , ab
'', 0
a', k' b', I' -. , . V. 19,
, / g i
,
(, d, e /) .
,
- , , , .
I II :

II

. IX. 10.,6,s.
2,3-
-.

(188);

M4 X 4 (S 12) M2 X 3 (6 //) .


(. IX. 10,), . ,
/MX / / ; , -;
, , '-^
;
- =
(. . IV). , -'
)
. ]
, - , (, -J-. )
/ AM , /MX / . ;
- |
188 / = 10,9, /MX =9,9 /AX 4,6 .

AI

Ai

MI

M
X

M
X

a
a

a
a

a
p

a
p

p
a

P
p

p
p

a
a

p
a

a
p

Xj

p
p

t p c i
a
a
P

a
p
a
p
p
a

p
P

p
a



.
, -
, , .
- , , . , , , AI MI,
M3, XI, X 2 /MX ( I) M2,
^4, X 3 X 4 / ( II).
-

, . ,
- AX B2

, -
. V 2 X, V 2 = Xi V 2 = X 2

.

(. . II. 5).
, ,

316

IX

317

. IX. 10, .
2,3-
(188).

-
,
.
. IX. 10, ,
AI, A2, X 3 X 4 II
,
AX. ,
AI A 2 ,
2 = 2(Ai A 2 ), X 3 X 4 |
, . IX. 10, .
II. - V 2 = (Aj J
2 )/2 , M H
. X 3 X 4
. "*
/ .

,
B2
.

2.3.


k

. ;
VA VB,
. VA ^
. BC
A-^-B
VB, T A
.

. IX. 11. 2- (189)


S2 - (190) (,
[7]).

. IX. 11
- 2- (189) (190), . - -

189

19

(|) B2 VOH (190), VOH (189) ,


(/>), / ( )
B2. ( f )
Mo.

: TIA
1 &.
1/TlA= 1 / T l A + 1 / T A

(IX. 4)

(IX. 5)

318

(t)

IS

(-

IfI
( /3

(IX. 5)
A

[ (- */,)] + M Z (t -> )

(IX. 7)

(/-* 0O) = AI^1C ( //,)

(IX. 8)

In

= t/f lA

const

(IX. 9)

,
In[ATz(O Mz (t-* )] t,
TIA ,
(IX. 5) (IX. 4) ,
Mz (t-+)/
(,
. IX. 11). TB (
),
.

-
.
,
. ,
. ,
[18]
.
(. 2.3 . VIII) .
2.4.
.
. .
, / S, ,
-
VS- -

X \

(IX. 6)

M* (t) = [ (- // 1 ) + 1 / 1 ]

M* (t)

319

IX

. IX. 12.
IS, .

/^\

yV

<v%, 0<

W Pa
^
-

,
.
, , ,
, . IX. 12. IS .
, .
- v/ v s . W , .
Wi W\ . ,
W2 W0, . W2 W0
, - InS. , . . (3)--(1) (4)*(2), - Bi VS, (3) (1), (4) (2) , . . (1)
(2) ,
(3) (4). , . . WQ,
(1), (4) .
, . . (4)->-(3) (2)->
->-(1), ,
(2) (3),

320

IX

(3)-(!)>-(4)->-(2). , .
, W0 > W2. , .

- . - |

.
, - , .
, :
, I
, - J
. , - >
E4, - -.'
, Ep^-E4-,
E4 -> . ,
(1) (4)
Na Nf1 , Wa$^$a Wpa^ap . ,

- -

- - * C

. ) ;

, , =

N JN^exp[-h(vs + v,)/kT]
(IX. 11).
hvs ^> /IV/, , /

.,
NJN6 = GXPi-Hv1IkT)
(IX. 12)|
if
$|
/IVs-


, ,
(
,

321

/(A)Z(XJ

(2) /3
. IX. 13.
//, .

. ,
, X . IX. 13, , Wo < W2.
,
- . . 3.1 . VII .
,
z- A, MZ ( AJo)
v:
Vx

2Wf

+W2+W0

YA

(IX. 13)

- , Wz, Wi Wo 1:(1/4):
:(1/6) =
50 %. , 1

. H 13C
(200 %), /7 = 4.

, -
, , 1/6. , , , -
.

, ,
, ,
11 .

IX

322

. 1
, -
. :
, VA VB,
, . ,
, .
- |
- f
(. . 1 . V I I I . 3 ?
). - 1
, i
. , - I
, - 1
. ; - ': (191) , 2-- ,
-4,4,6--1,3- - - (192
193 ). 191
( 2 6 % ) H 15
18.
4 193 12 %-
H2,
. 192
COOCH3

191

CH3 H2

CH3

192

193

, ,
,
- . , . , , CS2 CCI 4 .
,
.

323


, , . B2
, . 2 2
\2 ~ 1.
.
2.5. -
* ( ) , , .
, , -
B2, . \.
: , AMX, Bi, , . . ! M X B2. , ,
, . -
\,
, . B2.
I (. IX. 10, ),
VA > VM > V x / > /MX > /AX > , AMX
A j -, . IX. 14, . AI
V 2 . V 2 = MI,
. ;
. AI , * ( INDOR) internuclear double resonance. . .

324

Il
12

34

2 3
M

325

IX

Il Il

, 3 M4

X1 X 2 X 3 X 4

1 2 3 4
X

A 1
. IX. 14.
AMX V A > V M > V X H
- Ai.

( , , ( Ai. Xi X2, AI.


, , .
, , Bz
.
. IX. 15 - 2,3- (. . 2.2), Ai Aj.
- II (. IX. 10, ). 6 7 (M2 ), ,
-. , ,
-
. , ,
M X , ;
.
V 2 ,
-,
, , B2.

, . IX. 15, .
(. IX. 15, )
, BI

JL

. IX. 15. (), - (, ) ()


AMX 2,3- (188),

A 2 .
B2 , A 2 ,
,
. ,
. .
,

326

IX

. VII. vpq
, Eq, . , BZ, ,
Eq .
. IX. 10, ,
, , Np Nq; . ,
( ), ,
,
( ). vpo, .
M, vpq, ',z BI (. . VII. 2,6),
.
.
M
'. ,
BI (. . VII).

>

HCC

327

H^

H
^H.

NH

0,5.8.
1

. IX. 16. H [8].


; "N.

2.6.

,
.
, , V2 \\ . B2 , .
, - , , 1 H 19F
1
31
H P. , ,
14 N (. 4 . VIII
. IX. 16), .
- , 1H 19F, , , , . ,
19
F , ,
1
H( 1 9 F).

. IX. 17. 1 H () 1,2,3,4-


(); 100 (, [9]).

IX

328

15+
CH

H3C4+
C-H
H3C

--

CH3

WV^ W+Wv*r**r W*+


-132,8 .3.

13

. IX. 18. -- -.
-;
3 -.
''- '3CS:'. (. [1O]).

1 H( 2 H) (
H( 2 DJ)

. , . V I I I (. 2.3 . V I I I . V I I I . 9)
, -dn,
H,D .
. , '', 1,2,3,4-
1 H( 2 D) (. IX. 17).

-
.
1 H 1 1 H 1 3 C 1 1 H-KOH13
- 1,2-, C AMX (. 3
. V I ) . ,
. , ,
B2 . -
, -.
. IX. 18 - 13 - -, SO 2 ClF SbF5
20 0C 50 %-
13
C.
13C
13C 25 .
1

(
13
C )
,
2.7.

169-

+125,..

329

.

^ , .
B2 ,
.
( ),
, , 19F, . .
,
, . -

ii

L___j JL. Ii

1-

-1

} I

- -

37,5 -M.

. IX. i 9. '"F
( [U]).

330

IX

, .
. . IX. 19
19F(1H).

CO2, .
13C 1 3 C( 1 H),
. 13C,
. -, /. -, 1 H ,
13C, (IX. 13),
200 %. . X. 6.

331

=
-CH4

=
,C=C
H
H

C=Q

CH3

f^Y^^l^^
ff

2.8.
. X, 13C(1H), 13C. , , . , ,
- 1 H V2,
, . ,
. , , - , 13
C .
. IX. 4, (VA V 2 ), 15 10 . 13C 13C11H (,
) ,
.
13
1
C H
. (CH 3 ), (CH 2 ),
(CH) , , .
. IX 20.
, -

180

UO

100

60

20

. IX. 20. 13C , ,


167,6, 141,8, 96,8 20,2 . .
^- TMC ( ).
1 H; 5 1 H, 3 .

/ Av - J0:
Av==YB2./R(/2-/R)-1/2

(IX. 14)

1
13
, H C.
. X. ,
, ,
.
, (IX. 1).

332

IX. 1. ,
[12]
) A, X

- B-I
X 1

(/2) 2 3 > / /
( -

X)
(Y/2n) B2 ;

X
J_
( /2) B 2 = T2

:\

-
-

2.

3.
,

0)2 ()

(O1 >2 = const, B0 + AB , . .


X (O2(B2), MI (Bi)
(0/B2 = const, (Oi ;

X,
( O t ( B 1 )

(0!/B1 = const, (O2 ;


, B2 X.

15 , N{'H},
13
C(1H)
^
, - ,
; ;

-,

--

; -


; ; ;
-
(CCB);

()
)
( )


-; ; ; - ; , , 13C 15N,
-

; ; ;
, 13C

-,
, -

)
1. ,

. IX. 1

333

,
*
13C, . X.
, (. IX. 1),

.
.
3. -
,
,
. * gated decoupling. . .

IX

, , , -13 -15 (.
. I. 1), .
, -
(-) - (1
19
31
, H, F , , P), -, . ,
-, . VII, .
,
.

, , . , , ,
, . .
, ,
, : (-)
(-). ,
= 2 10 = 1024. 12 ,
,
--. 4
, -, 8
. - , ;
4 , .
,,
.
*;
. ( ,
) , 2, 7 = 2 -f- 2 1 -f- 22.
, 1 ,
, 2 ,
. ,
4 ,
, 15. 1
2
3
1111 (2 -f 2 + 2 + 2 ).
,
, 2"1. , .
,
-
, .
-
() ( ).

,

334

3.1. -.

- -, . IX. 21.
.
3.1.1. - . - , .
,
, -

. IX. 21. - -.

* bit binary digit. . .

335

336


. :
1) , ; 2) .
, 20 , , 12 , ,
10000/(2 1 2 1)=2,44 . .
, (
2,44 ), . ,
,
, , . . . 12- 2 1 2 : 1 =
= 4096 : 1; 4 16: 1. ,
. , ,
, .
-, ,

. (. . III) , ,
- ,
.

. , Av/, V 0 v;.
,
,
Av,-
. .
5 ,
10000 , 10 . , ,
5 , 2500 .
, ,
, -.

337

IX

(50OLT )

(WOO )

2ta

\ )

ta
(D,8192c)

( )

tdw

(8K)
4

(10~ s )

. IX. '11. -.

. t<iv, . . , . , 5 ^dw = 10~4 ,


100 . 8 ,
0,82 . . , , ,
, . , . ,
,
. , . IX. 22
.

,
,
. ,
- ()- 4 , 5 ,
1,22 ,
, .
,
.

IX

ULU P /
\unnyjit-\ <

339



-
(,6 T1
^, of)

'ii

I!

1
I
^

. IX. 24. - .

. IX. 23

, , , , , .

3.1.2. - - .
- ,
.
/, , 2
H CDCl 3 , C 6 D 6 . . ,

,
- . ,
- .
\,
tp (MKC),
90- . tp (90) 100 (. VII. 11).
90- . , ,
z-, - . ( 90-

340

IX

5 T i ) -1
-1
. (, ,]
^w) -|
:
-. , |
. , |
, ;
- \
. , ;
- ,
. IX. 24.

341'

4 OO
I

100

V
0

H3C-Cf
4
O-CH2-CH3

'
,

-CH3

H3C
}

C=P

TMC

CDCI3
_-_-. ~*~*~*~~~*~*^^

YMUAJIMJ <*- "* ** .

L*^^~~~.

3.2. ,
-
,
-
. , , , ,
. , Av -(- 6v. ,
, . , , ,
, Av 6v. , -
Av 6v. . IX. 25.

,
. ,
AVI.
. ,
V 0
. , , , .
, - (
) , , . , .
, , '

200

150

100

50

-50

. IX. 25. -.

G 13 -- 170,7, 60,4,
20,9 14,4 . . TMC , ,
.
YN 5000 Vo; (4000 ) , V N A v ; , .

. .

,
. , , , .
, ,
- ,
( 19 F, 3 1 P). , ; ,
- .

342

IX

- J
. , !
.
|
Av ?
. I
.
, -
.

-. , , . S1 , .

,
.
, \
z- .
, . - , .
3.3.
-

,
.
, , , 1 ,
.
. ,
( J T / N ) , TC ,
, JV . .
, ;
, *
. , |
, , *
/. -

343

1,25

"

. IX. 26. - 13 C-HMP .


/ ; ;
, ; .

. IX. 26,.
exp(/TC/W),
/.
, .
. ,
. .
, , .
,
. - ,
.

:344

IX

345

; . . 3 . I) .
, , . , (RiRz).
=12

4.1.
( )
CO2 - :
CO2

W.

L
7,3

7,6

t-

7,4

7,2 5

. 1 IX. 27. _
H,

; t = Q
( . f!31).

. 1|
,
. ,
-. . IX. 26,6.
4.

,
, , () *.
.
,
, ,
, (. IX. 27).
, , (
* CIDNP (chemically induced d y n a m i c nuclear polarization),
W d n a p . . .

. , ,
, . .
(So), .
.
S0,
,
. IX. 28,. Si B0, S2
B0. - 180, . B0 Si ( S2) , , (. . V I I ) . R 1 .

. IX. 28. B0
S0 , ; 180::
; T0 , 1;
0.

345

IX
1

Iv

If.

-^

(p. P^

Rl

R'-R

R2-

R X + R Y

. IX. 29. -*
(R 1 - -W).

R 2 , . !
-
|
cu = g^BB0///z

(IX. 15)^

g ( ^- ), a fj,B -',
.
*
<BI 2 *
Sj S2 (. IX. 28,6) , ,,,
, - {
(. IX. 28,). -,|
J0; Sj S2 , COB-J
. , ,
B0 --,
.

-'
. (. 2 . II)
( ). (CTB)
.
B0,
: , B0 - ( I), , B0 ( II)..
(I. 10) , coi > . -,:
, I -*
, II.
*.

347

, ,,
, . ,
(. IX. 29). , . . ,,
. II,
, >
I ,
.
;
. ,
, : I
, B0.
, ; . VH
. ,
. , .
4.2.
( )
( -).
. ,
.
(194) (195) , , - '
2,3,3- (196)
. , , , -
= , = 1
1.

,

IX

348
hv

((C6H5I2CN2

349

(C 6 Hs) 2 Ci

194

4C 6 H 5 I 2 C:

C 6 H 5 -CH 2 -COOCH 3

195

(C6H5J2C".

*/

-T-COOCH3

C 6 H;

X,

(C6Hs)2CIi-CH-COOCHj

A2

X2

C6H5

196

^-. , ,
.
, , , . , 195
( R i - -R 2 ) . AX , , pp.
CTB ,

PP
, .
. ,
C6H5 C6H5
C6H5-C-C-COOCH3

80

60

40

Hg

. IX. 30. f
- 2,2,3- , |#
*

14O 0 C ( *
. [14]).
''

A.

X2

A,

X,

. IX. 31. AX.


G ; ;


, coi =
= (-(-1/2) Co2 = (1/2),
. - , , (.
, . IX. 30,
. IX. 31, , - .
,
, ,
. IX 31,6. ,
|3 = 1
.
,
, -
.
, ,

350

-1
, .
4.3.
,
. ,
, . ,
, . , (-, + , )
= Ago,

(IX. 16)

. , (196) : CTB
,
/(,) , , i /
(CT,-/ = ),
/ ( =
= -). () = ,(+) ( + ) ( + ) ( + ) ( ) > . .

. -
,
.
, ,
. ,
, -
(197) (198),
Li

( , + ,
/, /)
=

351

IX

(IX. 17)

, :
Ji :
+

K1 :
+

kg. g{ g (g- ), g{ '-
CTB ()
/ ( ., - ()
.. , '- /-
:
+ i /
i /

/,-/ (. 2.2 5.1).


, (IX. 16)
(IX. 17) .
, , , /// // - !
, , ',
,

9.

0 ,1

[C6H5-CH-O: R'J -i

C6H5-CH-O-R1

[C6H5-CH-OLi -R1J

-C6H5-CH-OLi

R1
197

Li

[C6H5-CH=O 0IR1J '

198

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

, 102103
- .

352

IX

353

5.

6.1.
. VII , , ,
. ,

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

R"

_I_ D -> P -J- *"


- *
*\ "T

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

. .
,

,

a = Qp

(IX. 18)

Q , 0,025 T,
( ,
T (). ^ JLI-M - = 2 ( ,
CH^ 1Fx - ;
;
, . , ,

. IX. 32. H l-w-



- [R I ( , -
[15]).

R ; -cU;
S .

2 - :

ib /

,
AX
12 X.

354

IX

(A , X )
. , , , , .
, - (R'~) (R) . (. 1 . V I I I ) , ,
,
. , . ,
, .
.
/zvs (CM. . 2.4) /zvi ,
( = -f-1/2)
(N+1/2 > ^/-1/2) v
V = N+1/2V+1/2 + N- 1/2V- 1/2

(IX. 19)



/ = afefi/4ypkT

(IX. 20)

Ye Yp , k , T - , v
. , (IX. 20)
, .
. IX. 32
1-- (199)
-.

(3

CH 2 CH 2 CH 3

- - > 27,
, ,
,
2 - .
, (IX. 20),
(. 199). , . ,
1/6,

355

.
2 - .
- , (. IX. 32). , , 199.

,
, .

.
5.2. .
(-)

, ,
. , . , , .
.


(3cos 2 9 I)//" 3 ,
,


pa- \
- .
-^) BQHUB
,
. IX. 33.
''
. IX. 33. .

12*

356

IX

,20

1 2 1 1

. IX. 34. 1H -2 [16]. .



().

()>

, . , ,
(III)

200 [()-Eu(III) Eu(DPM) 3 ], (III) (5-, - /H3 H3C
CH3
.
X
CH2

, '
\3
(3cos 2 0
1 ).

. ,
2OO
-, , ,
.
B0 , . - ,
, -2 (. IX. 34). - ,
. ,
, , .

357


,
,
.
.
. E u ( I I I ) ,
. IX. 33, P r ( I I I ) , .
,
: NH 2 > >
> = > COOR > CN.

(., , . IX. 2). ,
,
. ,

.
,
. , , (. . IX. 2).
( 1 H 13C) , LIS- *,

/ , . . (IX. 21)
1 H 13C , . . . ,
, ,
.
. , , . , . IX. 35 ,

[4,4,1]-1,3,5--11 ,
* LIS i a i i t a n i d e
induced shifts. . .

358

IX. 2.

Eu
9

O O

w+

3^ ,1
1^CH3
CH3

H3C

XF 2 CF 2 CF 3

H3C-

3+

Pr3+

H3COOC4^H

COOCH 3

1,4

( H)
3
('H.
' C)
30

B--

1,2

(B]

1,0

H3C

DPM'

1,6

/^fi^^i

359

IX

FOD'

.CHI ( :

0,8

- .-; FOD-- 1,1,1,2,2,


3,3--7,7--4,6--

0,6

0,4

CHz ()

0,2

()

DEHD" 1,1,1,5,5,6,6,7,7,7--2,4-;
- D-

3--

0,10

0,15

0,20

0,25

MK/^S
.

DPM

0,05

FOD

,
;

- TMC,

- .


, ,

0,7)0

. IX. 35. ,
Eu(FOD)s, 1 H - - 11-[4,4,1]-1,3,5- ( [Fisher H., Diplomarbeit Universitat KoIn,
1978]).
()/.

.

.
(. 2 . VI) D- L- ,
- .
. ,
. IX. 2.
6.

,
-

; , . ,

360

IX

361

. IX. 36.



. ;

. , , 2040 0C
, , .
. ,
(. IX. 36),
, . , , 4,4- (201) -(-4- (202).
H3CO

OCH3

2Ol

C 2 H 5 O-

22

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

.^^^^7 ,

+S W*-^
20,

^V

4000

. IX. 37. 1H () () ( 202 ).

. , , ,
. .
. . IX. 37 2 - . ;
202 4000 .
, ,
A 2 (. . V. 2).
,
^^- \ E^-+E^
(. IX. 38, ). [2,
r\z, ,
.
*

(IX. 22)
/4 .

362

2 B0+ 4Ei

-2 .

. IX. 38. 2.

T] 2 -- (. . IX. 38, ).
(1.2),
(IX. 22) :

(IX. 23)
,, (+ Pa)/2, PP,
Ui = 2 (. . ) (1) (4) Af^ 4 :
A f 1 4 = (1/4) 22 (3COS 2 Q- I)Tf 2 3
(IX. 24)
(2) AE2:
2
2
2
3
AE2 = ( 1/2) Y A (3COS G- I)Tf 2

(IX. 25)

G (. . IX. 38) - Ti 2 B0.


v = V 0 3/4Y2 (/42) (3 COS 2 G- 1) Tf 2 3
v = V 0 (3/2) Z)12

363

IX


A 2 .
(IX. 30),
\2. Si1-,

. ,
A 2 :
S\z fi2- , 4000 , (. . IX. 37), , (IX. 23),
D\2, 1333 , , ,
. .
,
- ,
, - . , .
,
, ,
, , ,
13C.
, , , , . ,
,
.

(IX. 26)
(IX. 27)

-/ :
2
2
2
3
D11 = (- / /4 ) (1/2) (3 COS G - 1) r~
(IX. 28)
,
S1, = (1/2) (3 COs 2 G - 1)
(IX. 29)

/> = (-AvW) Vu

( - )

1000

. IX. 39. H ( [17]).

364

-*
, - .
:
50 (. IX. 39).
,
, . V,
- - .

'=z V1/; ( + z z (J1, + 2D17) J2 (i)iz a)Kl

+ Z Z (J1, - D17-) (Tx d) Tx (i) + d) (/)]

(IX.31)

v,- , ,
. , ,-/ ;/ + DU,
,-/ Di/.
, ( I X . 3 1 ) .
,
. ,

- , . , ,
,

-

. ,
. ,
, , , .
, BO, .
.
7.
. I,
. ,
- - (. . 2.4

365

. IV) . ,
, , ,
, .
,
- .
, , - . , ,
- , .
:
. , , 5444' (
), .
cos Qi1- ,
(Qa ; . . IX. 38). (3cos 2 p1); P = 5544',
, cos2 5444' = 1/3.
, ,
, , , .
, , ,
. 10 , . IX. 40.

-, ,
(
).
90-,
WAHUHA*, : Px' 2 _' Py' 2 _,/ , Pi
* : Vfaugh, , Waeberlen,

/X

.
_1

40

19

- - '

(
)
(KPF 6 ) (
. [18]).

;
, 8 ;

, - 1 '''F .

i- .
. IX. 41,

. 6,
T2. , tp
. i 10 , tp ^
^ 1 . ,
, .
, ,

.
,
/( 1 3 C), S,
( 1 H). .
8/ 6s, ,
, G 5

'

t=

. IX. 41. W A H U M A
( . [19]).

367

S 6/ .
- .
S / , S . / ,
. ,
-, , , .
8. -
,

(. . 7).
( ) , ( , , . .)
, .
,

. , - ( : - *, ), , , -, ,
.
1973 . -
.
B0 + AB,
. , , .
,
, ,
, .
.
* \', , .

368

IX

-,
, 1 ,
H 2 O D 2 O ( 5 ) .
'H . IX. 42. . IX. 43.
- , .
.

.
, , -.
;
;
, ,
. ,
- , . ,
. , , . IX.44
. , -

369

. IX. 43. -, ,
. IX. 37 ( [21]).
1 , , 4,2 , H^O DsO.

. IX. 42.

-
H2O

,
( [2O])

!
, -
. , ,
.
-, ,
, - .

*.
- - , ,
* ,
- . : Mansfield P., Morris P. G. NMR
Imaging in B i o m c d i c i n e , Acad. Press, N. Y., 1982. , nepep.

370

IX

371

16. Technical Bulletin, No. 4, Varian Associates, Palo Alto, Calif.


17. Saupe A., Angew. Chemie, 80, 99 (1968).
18. Endrew E. R., Firth M., Jasinski A., Randall P. J., Phys. Lett., 31A; 446
(1970).
19. Waugh J. S., Huber L. M., Haeberlen U., Phys. Rev., Letters, 20, 180 (1968).
20. Lauterbur P. C. Nature, 242, 190 (1973).
21. Lauterbur P. C., Pure Appl Chem., 40, 149 (1974).
22. Endrew E. R., private communication.

:

37,

40,

41,

50,

52.


) Johnson L. F., Superconducting Magnets ( [2], . ).
) Hoffman
R. A., Forsen S., High Resolution Nuclear Magnetic Resonance
Double and Multiple Resonance. . 74, T. 1.
) Philipsborn W V., Methoden and Anwendungen der Kernmagnetischen Doppelresonanz. Angew. Chem., 83, 470 (1971); Angew. Chem. Int. Ed., 10, 472
(1971).
,
r) Reynolds G. F., Nuclear Magnetic Resonance Using Weak Perturbing Fields,
J. Chem. Educ., 54, 390 (1977).
) Kennwell P. D., Applications of the Nuclear Overhauser Effects in Organic
Chemistry, J. Chem. Educ., 47, 278 (1970).
) Backers G. E., Schaefer T., A p p l i c a t i o n s of the I n t r a m o l e c u l a r Nuclear Overhauser Effect in Structural Organic Chemistry, Chem. Rev., 71, 617 (1971).
) Bremser W., Hill H. P. W., Freeman R., Die Technik der Fourier T r a n s f o r mation in der hochauflosenden Kernresonanzspektroskopie, Messtechnik, 14
(1971).
) Cooper 1. W., The Computer in Fourier Transform NMR. . 75, T. 2.
) Pine S. H., Chemically Induced Dynamic Nuclear Polarization, J. Chem.
Educ., 49, 664 (1972).
) Seifert
K.-G., Chemische induzirte dynamische Kernspin-Polarization
(CIDNP), Chem. Unserer Zeit, 10, 84 (1976).
) Lawler R. G., Chemically Induced Dynamic Nuclear Polarization. . 74,

. IX. 44. . '-- 7 . ( . [221).


, , 2 .
5 , 0,5 , ,
. , .
: . ,
-. ,
-,

, , 19F
31P. , -.

T. 9.

4) Spencer T. S. O'Donnel C. M. CIDNP Experiment Using a Permanent Magnet, J. Chem. Educ., 50, 152 (1973).
H) Amman R. V., Fischer R. D., Verschiebungsreagentien in der NMR-Spectroscopie, Angew. Chemie, 84, 737 (1972), Angew. Int. Ed., 11, 675 (1972).
Petersen M. R., Jr., WaM G. H., Jr., Lanthanide NMP Shift Reagents, J.
Chem. Ed., 49, 790 (1972).
n) Hofer O., The Lanthanide Induced S h i f t Technique, Application in Conformational Analysis. In: N. L. Allinger and E. L. EHeI (Editors), Topics in
Stereochemistry, vol. 2, Interscience, N. Y., 1969.
p) Reuben J., Paramagnetic Lanthanide Shift Reagents in NMR-Spectroscopy,
Principles, Methodology and Applications. . 74, T. 9.
c) Saupe A., Neuere Ergebnisse auf dem Gebiet der flussigen Kristall, A n g e w .
Chem., 80, 9 (1968); Angew. Chem. Int. Ed. 7, 97 (1968).
T) Diehl P., Khetrapal C. L., NMR Studies of Molecular Oriented in the Nematic Phase of Liquid Srystals. In: B76, t. 1.
y) Khetrapal C. L., Kunwar A. C., Tracey A. S., Diehl P., Nuclear Magnetic
Resonance Studies in Lyotropic Liquid Crystals. . 76, T. 9.
) Nachod F. C., Zuckerman I. J. (Editors), Determination of Organic Structures by Physical Methods, vol. 4, Academ. Press, N. Y., 1971.

*
1. Varian Assosiates, Palo Alto, Cahi
2. Johnson L. F., Anal. Chem., 43, 28A (1971).
3. Anet F. A. L, Bradley C. H., Bradley M. A., Brown M. A., Mock W. L
McCausland J. H., J. Am Chem. Soc., 91, 7782 (1969).
4. Vogel E., Kldrner F.-G., personal communication; Klarner F.-G., Dissertation, Cologne, 1968.
5. Ounther H., Wenzl R., Grimme W., J. Am. Chem. Soc., 91, 3808 (1969).
6. Hoffman R. A., Forsen S. . 74, T. 1.
7. Forsen S., Hoffman R. A., J. Chem. Phys., 39, 2892 (1963).
8. Technical B u l l e t i n , Joel-Kontron Co., Munich, BRD.
9. Pawliczek J. B., Gunther H., Tetrahedron, 26, 1755 (1970).
10. Olah G. A., While A. M., J. Am. Chem. Soc., 91, 5801 (1969).
11. Ernst R. R., J. Chem. Phys., 45, 3845 (1966).
12. Philipsborn W. V., Angew. Chemie, 83, 470 (1971).
13. Bargon L, Fischer H., Johnsen U., Z Naturforsch., 22a, 1551 (1967).
14. Class G. L, Class L. E., J. Am. Chem. Soc., 91, 4549 (1969).
15. De Boer E., McLean C., MoI. Phys,, 9, 191 (1966).
* .
.

-19 -13

X

-19 -13

. -19 -13.

19 F
, 19 F 1 H ,
.
13C ,
.
, 13C , . . X. 1.
/ = 1/2, .
, 19 F .
13C . ,
.
13 C 5600 . ,
13C .
- X. 1. 1 H, 13C 19F

13
19F

1/2
1/2
1/2

100
1,59
83,3

V3,

,
%

99,98

1,11

100,00

1,41 T

2,35 T

60,0
15,1
56,4

100,0
25,1
94,1

373

-13
-' , , .

- . 1 H
19
F ( ),
.
-13 , , . (. VI1.6)
. . 2 , , ,
13C ,
.
1. 19F
1.1.
1 H 19F,
.
10 . ., ,
500 . . ,
1000 . . (. X. 1).
.
. 1 . II, . S0 , . ,
(~1 %).
, ,
r2u2

NOF

865

476

CF3OF CFCl 3 HF CH 3 F

140,5
9

. X. 1. '- F.

-192 -276

8,

374

CFCl,

C6H5CF3
CF 4 CF 5 CO'
=C

CFCU
+430

375

-19 -13

-6 -77

CF
-163 ..

, .
19 F (CFCl 3 ).
, ,
-
, . ,
. , .
. X. 2 :
ScFCl 3 = Sc 6 H 5 CF 3 63 M. . =

= SCK, 64 . . =
= ScF3COOH 77 . . =
= 6 ' 163 . . =
= ,.-2 + 430 . .
, .
,
, , 5 . .
CFCl 3
- , -
. 19F
. X. 3.
CFCl 3 - .
I
CF3, =CF2, F.

. -

. X. 2.
19
F.

-50

"'2

-100

. X. 3. -

18

-200

-300 ,..

F .

, , F ,
,
F-. ,
. ,
'-
, .
, , ,
, . 19 F
. . X. 2
.
, 1 9 F. ,

E.
, ,
.
19F :
0

CFCl 3

NF3

CF 4

BF 3

ClF 3

PF3

SiF 4

142

-64

-129

83

37

-172

3,0

2,5

2,0

3,0

2,1

,
,
19
: - CF 4 ,
CF 3 Cl:
CF3-F

CF 3 -Cl

CF3-Br

CF3-I

19 F,
. 1 9 F CF 4 -

X. 2.
6

( CFCl 3 '

19

' M

CH3F
CH3CH2F
CeHsCI-^-F

-276
215
207

-151

J
- >
- )

CF 2 Cl-CF 2 CFCl 2
64,8

-19 -13

376

133

-124,0

114,0 71,0

F2 -"

Cl 3 C-CF 2 -CCl 3

-98,0

CF3-CF2-CF2-CF3

-84 -129
^UC-CHF=CHF

-165

rpac-CHF=CHF

-186

F
' /-120,9
-219,4 V-126, 2
/
\_/
/

* F
F2 -121,6
-221,1

R=H
Cl
C6H5
F 1 103 -105 -102
F 2 -127 -121 -133
F 3 -185 -145 -193

. - , .
, . .
(. 1.6 . I V ) . , CF3 , --,
( )
CF 3
I

CF 3
|

CF3-C-F

CF3-C-CF3
|
CF 3

I
CF 3

6 = -76
6= -63
- F, Cl, Br I :
X =F

-106,3

-101

= CL
-Br
=1

-107,9
F -133
F. JL ,F -161,2

-87,8

C 6 H 5 CF 2 Cl

49,4

C 6 H 5 Cf 2

-137

+12,0

CFCl 3 CF4 CFH3 ( .. CF 4 ):


CF 4

CF 3 Cl

CF 2 Cl 2

CFCI 3

36,8

60,4

CF 4

CF 3 H

CF 3 H 2

CFH 3

-18,2

-80,0

210,0

76,7

,
, . ,

377

CFCL 3 =-132

- -109
= -100
= -87

, 19F . ,
, ,
.
19 F . ,
- , , , :
CT = CT1 + (TR

(X. 1)

(X. 2) (X. 3), \ OK - -:


(X. 2)
_ (5,83 0,26)
(X. 3)
= - 5,83 Z . - (18,80 0,81) CTR + 0,8
3,4- 3,5- , 19 F /=

378

-2^2,5

-19 -13

-243,5

V(F.)

-106,5

-107,5

-108,5

-9,5

1,1,4- 4- - "F CH-F; - .

379

-. -
.

19F . (. . 1.2 . IV . 2.2.1 ). ,
.
, . , ,
.
19F - 19F, 19 F 19 F, 1 H. - .
19F, \, \,
- 4--1, . X. 4, , . - 1H, 1H 19 F, 19 F 1015 ,
50100 . 19F
, .
,
,
, , , 19F. , 19F

. ,

19
6v. . X. 5 F 1,2- .
A 2 . - ,
- '.

*. = 40,3 / (9,65 /).
=
1
= 510 30 /"
(122 7 /),
- .
19
F
, 1,1-, -

380
CL

19 F , , ,
. ,

,
.

Cl

Cl-T^ F

cijjci
F

-12O 0 C

381

-19 -13

. X. 5. 1,2-.

56,4 (,
).

15,6 . ., 30 ,
. -
. 810C - - 2,2- (203 204).
63 / (15 /). , 2 -
(205)
. ABX A 2 X
, (205').

1.2. -
19
1
19
F, F H, 19F
, -
X. 3. -
19
19
1
19
F, F H, F ()

CH3
C ^ 2 A-C-GOOCH 3

CH3
187

Cl 2

47,9

49

/-J

244/

54,6

203

204

2-4

CF 2 Br-CCl 2 Br

155,8

v_
c r c/

F
H

F' - v

54,7
72,7

382

. 1 H 1 1 9 F 19 F,1 9 F. ,
' 9 F 1 1 9 F 1 H 1 1 9 F .. 3 X. 5. , ,
.
X. 4. -
19
F, 19F 1 H, 19F ()

CF-CF 2 -CF 2 -NF 2

CF3-CW3

.12,8

(CFj) 3 CF

'CHj) 3 -CF

20,4

CF 3 -CF 2 -COOH

383

-19 -13

X. 5. -
F 1H, 19F ()

19

C F2-CF2- CF2- COOH


4
F1 _ CF,
3
_/
\ ,
F
F

CH 3 -CH 2 - F

V(1, 4)
V(2,4)

22
8

7.J4

V(3,4)

13

Br, J[ .F
J U 5

c-c

L/

yT)[o/r>-2Qoa .
^^*^"

\4

9,9

18

19

F,

25,7

xH

3,5

\,.

ck - (
^^^^F

/^ 2

1|
F

" -

772

- "'
Br

H1F

16,4

19,4

FN

> t

c=c

Cl^

F
CL

^C

X
4

-2

H
-18,7

20,4

-124,8

4,4

Cl

/CL
4

(-) 129,6

19-25

17,7
6,3

8,3

, -
,
,
.
, 19
19
F 1 F
, .
. 2.4. . IV,
, - ( ).
-
19
^F 1 F .
300 . , ,
, CF2.
, ,
1
1
- H 1 H, 19
19
F 1 F, : s- C-F 2 / F ,F .

384

- , .
, , -
, - ,
1 9 F 1 1 9 F. . X. 5,
- 10
.
6
JrPOHc > 1 -, .
- 1 9 F 1 1 9 F , ,
, 1 9 F 1 1 9 F . ,
/F?F > /, > /-
, .
, - -J-5 +20 , - 20
+20 , - 20 .
, -

.
VFF

, .
1,3- , .
4,4'- , 170 .
,
, . , -
(. X. 5).

19F, 19F
.
206 207
3Jp, F,
. , 19 F 1 19 F, ,

-19 -13

CL

Fx

ci

ci

2O6

=-1,3

385

= + 8,3
= -5,8
(

CL

2O7

,
.
, , - 19F .
- ,
.
1 H) 19 F, ,
19 F 1 19 F. 1 H 1 19 F . X. 3 X. 5.
1 H 1 19 F (50
+ 10 ), -.
, 3 / ,
, (. 2.2.1 . IV).

3

- /H,F={

31 cos2
0<<<90
44 cos2 90<</>< 180

(X. 4)

19F, 19F, , -
1H, 19F
(. X. 5).
13

2. C

-
13C, , , .
13C .
B0 . 13 X.

386

387

-19 -13

-2,5

Ci,6

C7

TMC

Cy3

_L

_L

_L

180

160

IAO

120

100

80

60

40

20

13

. X. 7. - C .
19F
/.

..

.
X. 6. 13C .
, 64 320 ,
22,63 [3]; 15 ;
,
- [4].

^^

. , .
/, 13C
, 13C
( 15 ).
13C . ,
/. ,

, , . X. 6.
, ,
/ UM-

- (-)



. :
13
_. . X. 7 C ,.
.
,
13
C , . , - 13
, , C
, . , (C = N,.
C=O, C=NR . .), . , , 250 . ., ( 1 H) (0,3 ) .
13C .
13*

388

-138,2

389

-19 -13

-181,5

. X. 8. 13C (),
1 ( . [5]).

A 4=fc B, . , ,

, . , ,
, ( ). 13C
,
.
6v 13C .
13C.

, 14C, 13C. ,
, , , 13C, .
(2) (5)

,6)

; ;
26 . C3-C5 C 17 .

, .
.
,

.
, . X. 8,
.
, 13C
1
H,
.
. 1 H 13C

, , - .
13
C, . -,
, ,
13C, , .
-

fi-CH3
i
J

/ CH3,
' _ '

250

V
'

350

. X. 9. 7\
- ( . [61).

13

C -

180 90",
( ) 2 .

390

-19 -13

391

13

C, 13C, . . 12C.

13
C.
, - ( 13 , 13 ; 13 C, 1 H; 13 C 1 X X = 19 F, 31P
. .) 13C - \. - TI .
(. 4.1 . V I I ) . X. 9.
(1/T1)
.
. TI
.
,
- .
2.1.

13C
, 13C .
. IX, - 13 -. TMC
(. . 2.2) , 2H CDCl 3 .
, ,
. , , . -,
-
13
1
C 1 H, . . . -,
, .
, .
2.1.2. .
,

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

BZ- ,
. X. 10.
(. X . 1 0 , )
.
. ,
. - 13C11H,
.
,
(. X. 10, ).

\ KU
. X. 10.
.

"U
. .

392

(J

,
.
, - , , , . () , .
, , .
- 13C, ,
(. 2.4. . IX). , , , 13C.
2.1.2. .
13C .
. ,
1 H
.
. 2.8 . IX . IX. 20, , , . , 1 H 1 1 3 C.
, ,
(. . V).
-
,
, 13C
13
1
. /( C) H)
, , .
, V ( 1 3 C 7 1 H ) 161 ,
125 .
13
C.
-

2--4- . X. 11. . C2 4 ,

393

-19 -13

CX

CJ

SS

03

Il
CU

394

Cg Ci 0 -
H (7) H (6) , C 6
C 7 1J(13C, 1 H)
2 J( 1 3 C, 1 H). ,
.
, , .
,
.
13C11H, 13 - . B2 , '/( 1 3 C 1 1 H) (. ). , - .

B2 .

-. .
13 C- '-
. / R
Av. (IX. 14),
/ 2
2 \ ^ /^
Av /R (Jo / R ) ,
13
C.
Av = . 8 , ,
,
-. ,
(. . 2) 6(CH 2 )
2,15; () 5,35; 6(Hp) 6,10; 6(H Y ) 6,42 . . :
2,20; 5,26; 6,09 6,50 . . .

, , ,
. ,
, 2 - .

-19 -13

395

-2 C-S -3 C-A

. X. 12.
13
1
C-( H) -1,6, C^ (,
[8]).

750 730 710 690 670 650

- 13C12H
13C 1 : 1 : 1 . . , , ,
(. . VI), /( 1 3 C 1 2 H) = /( 13 , 1 )/6,5144.
, ; .
. . X. 12 -1,6, 4.
, ,
C3 4. ,
C3 C 4 . -
C4 0,3 . .
.
C 3 , ,
(0,1 . .). 2 Cs;
- /( 1 3 C 1 2 H).
, , , , 13C
\. - H,

, , . . -

396

397

-19 -13

\ ( ) :
'X-I

-200

5,4 5,4

2.2.

X-CL

13C 250 . .,
, 650 . .
. X. 13.
, -
ld
C , .
, .
,

13
C (TMC).
, - 13C
. , 13C

200

X-Br

''9- '

150

100

i
50

-50

. X. 14.
13C ( [9]).


(. XI).

2.2.1. .
6( 1 3 C) ,
(II. 4),
:
' (T

i _.r
- <7naDa ~\~

/ v \
\ . Of

, 13C
. , , .
;
, ,
, ;

(X. 6)

C-CH 3

--
i

V0 <
1

+ 50

-50

,
-100

C-O

i
-150

QcH2),
I
-200

. X. 13. 13C .

I
-250

Zj /, Ri1- , .
,

.
,
(. X. 14).

L-(-V)

Q|/

(X. 7>

398

, , 2-, a Q 1 -/ ,
-.
,
. . (X. 7)
, .
,
(0--*, -*-*, ->*, n -- *
>- *), -> *,
. .
13C
.
->,*
. .
, , , :
H3C

CH3

H 2 C = CH2

H 2 C=C=CH 2

5,9

Qu = ,

V^

QtI=O)S.
i^i

399

-19 -13

213,5

HC=CH

71,9

11

, ,
,
,
Y I hp' . ( ) , .
, . 13C . .
, 13C -

1,500
1,200
1,100

<

1,000

0,900
800

0,700
0,600
0,500
0,400

200

190

180

170 160 150

130

120

100

9.0

80

&0,..(<)
. X. 15. 13C -
(, [1O]).

-
:
= 160
(X. 8)

. IX. 15.
(X.8) , ( I V . 2 ) . , , .
(X. 8)
,
60
360. , , (X. 7) .
, - ,,
a-. ,
(X. 8), 13 .
C
, .

400

-19 -13

q 12

20

. X. 16. 1H 13C -- 19F /- . 0


(, [11]).


. :
2,5 19A 1 O

CH 2 -CHQ-.

==0

opro- .
19
F,
, . . X. 16
1 H 13C /-
,
19F - .
, , ,
-
13C.
, 13C , .
. X. 17.
, 13C , 13C .
. X. 18 13C .

. ,
4 3,5

S =24,..
= 0,218

>

.0

S 149,8128,4

401

4,5 -
- 2

13C,
- :

./3
N(CH 3 I 2 L

OCH 3

CH 3

= 28,9..
NO2

140

..

X 17 13C
; A Q n /2 (, [12]).

402

X
-19 -13

. . IX. 18.
13C .
. X. 6,
, , , , ,
,
.
. ,

.
13C ,
.
, , 208, 50 % -13 2, 1 60, . ,
209.

- 3,5

. X. 18.

(,
[13]).

140
135
8, ..

. - . ,
, . -> *
v * AE. ,
, ,
.
, , 13C X. 6.
13C
(, M. .)

-
CH 3

(CH3J3C

32

47

318

60

(CHj)2C C2H5

332

43

(,)2-<]

280

27

C6H5C(CH3I2

254

(C6H5I2CCH3

198

(C6H5J3C

211

208

(CH3 )2
+

403

2-

\
*-

209

-
CH 3

'

208'

, '
(X. 5). , Aa
AX .
, . 1 . .
13C . , . ,
( 1 3 C)-
. ,
6'( 1 3 C) ,
-.

404

-19 -13

.
,
- ,
, . , Aa
, ,
(IV. 14), . , , , ^-,
, .
2-2.2. .
13C
,
13C.
,
, , .
. - - 9 10 . .
- 2,5 . .
211 212 213 210
. ,

:

(,) = + ]
H3- CH 2 -CH 2 - CH 3

1, 23,

. H'

CH 3 /

C H j C H 2 - CH2- - 3

22,7

210

(X. 9)

->"H 3

22,3 30,2 32,1 ,8


212

211

CH 3 -C-CH 2 -CH 3

C H 3 30,7
37,0
29,2


( 2,3), AJ a-, (3-
-, / .

= +9,1, = +9,4 *, = 2,6 . .
, , .
,
. ( 27,6)
:
-
|3-
-

9,0

213

+ 1,4
+5,4
6,4

+6,0
9,0


,
13C
. :
214 2146, a-
.

80,2

214

2145

, ,
(123,2 . .). - ( Cp ' ):
Aa-:

, 6

405

+0.4 -6,8-7,7

+6,5 +1,6 -1,1

/~ ~ - C-= - CCT- 0- /'

, .
. '

. X. 7. 13C
(. XI).

406

-19 -13

X. 7. (. .) 13C , [14]

F
Cl
Br
I
OR
OCOCH3
NR2
NO2
CN
COOH
CHO
CH=CH2
C=CH
C6H5

70,1
31,0
18,9
7,2
49,0
52,0
28,3
61,6
3,1
20,1
29,9
21,5
4,4
22,1
9,1

7,8
10,0
11,0
10,9
10,1
6,5
11,3
3,1
2,4
2,0
-0,6
6,9
5,6
9,3
9,4

-6,8
-5,1
-3,8
1,5
-6,2
-6,0
-5,1
4.6
3,3
2,8
2,7
-2,1
-3,4
-2,6
-2,5

24,9
2,0
7,9
-38,1
29,4
18,2

34,3
-6,1
-1,4
7,0
-38,9
-27,1

22,3
-15
4,2
13,6
14,8

-0,9
+ 15
8,9
13,2
-5,8

35,1
6,4
-5,4
-32,3
30,2
23
22,4
19,6
-16,0
2,4
9,0
7,6
-6,1
13,0
9,3

12,5
12,9

'H

-11,0
-7,4

-14,3
0,2
3,3
9,9
-14,7
6
-IFJ
-5,3
3,5
1,6
1,2
1,8
3,8
1,1
0,6

0,9
1,0
2,2
2,6
0,9
1
0,8
0,8
0,7
-0,1
1,2
-1,8
0,4
0,5


-, . .
- (.
- ). ,
, , . . X. 8, , 13

X. 8. - - (, . .)

70,4

30, 7

33 21,0
18,7

17,3

.C=C'

10

35,0

C=C

, 215

407

38,7

215

, -, , , .
^- .
2.3. -
-13
-
13 C: 1 3 C, 1 3 C; 1 3 C 1 1 H
13
C 1 X, X .
, .
-,

-
13
C113C , 13C, .
1 3 -
13C.
-, 13
1
C, H,
. ,
. III,
13C. - .
, .132.
19
31
, C 1 X, X = F, P . .,
13
C
.

2.3.1. - 13 C
. , . X. 9,
, - 13C,

408

CcHr
^->65

H
12

34 6
676
171,5

70
43

H3C-C=N

57,3

T T

/^LJ

CbI -C-X
r v
3
l

/
4

T^*

C6H5-HC=CH
2
'C6H5-C-CH3
[|
f

-19 -13

s-
2 sp^- s(i)= 1/(I + , 2 ).

X. 9. -

H3C-CH3
H2C=CH2
HC=CH

im
13

13

C 1 C ()

..

^_

X = CH3

36,9

37>I

39,5
Cl
^1
Br

40
tu,
U
40,2

H 2 C 4 ^X

H2C/ \Y

H 12.9

C1

,3,3

Cl 15,5

II
J
$
"

13

409

X. 10. - C, H
()

^-^
^

H
/*
C=C
/
\
\\
H

H4

125

157

HC=CW

250

13

&

13

C , .
5- <$ /, - C1-C/:
'/ ( 13 C, 13C) = 55Os (O s (J)
(X. 10)

(1)

,
, - , ,
. (
), s-
. :
CH2=C=CH2
31,3),,

98,7

11 L
2 3~6

23,2

(D
(2)

202

(3)

152

13?

142
H

220
95,2
- L-J.
''

s- .
- 13 C 1 1 H '/ (13C,1 H),
. X. 10.
'/(' 3 C, 1H) = SOOs(I)

164

(2)

190

1.1-1
6 4~24

178,5

161

(X. 11)

(X. 10) (,
s(j)= I ls- ),
s- s ( i ) H, . '/(' 3 C) 1 H),
,

170

200

COOR
J/V

160

ROOG
1

W H

/V
/fl/7
^JK

*H

(D 135,5
d) 146
(3)
172,5

162
158
159

CW 5 Cl

151

CW2CL2

176

CWCl3

209

410

-19 -13

, CTb '/( 1 3 C, 1 H) , . ,
13
1
'/( C 1 H). 2
161 , H -
,
. (X. 11) ,
s- , H, 32 %, sp2, '-.
- - (82 %).

13C1H.
, ,
,
. , '/( 1 3 C, 1 H)
. , ,
. X. 10. ,

.
- 13 C, 1 H, ,
, , 20 .
, 13 - , 12 C, 13C .
-
13
19
13
1
C F , C H.
170 400 .
13
1
'/( C 1 H) ,
-

(-)
13
1
'/( C 1 H).
2.4.
-
13 C
- -

. . VII, 13 C
. X. 9.

41J

,
?
. V I I , -
, , . ,
.
,
- . ,
, (I. 12).
6, 6, .
13C ,
.
, R?D = (l/Ti) DD
DD

-6

(X. 12)

.


500 10~"' .
, (X. 12) . ,
.
T),-
(),
.
. IX, TI = (1/2) (YH/YC) = 1,988.
,

= -f<^8 ' 100 ( % )
1,988

100

(X. 13)
(X. 14)

412

R?D
\ ,
. 2.1.2. \ ,
CH, CH2 CH3, 20100 120 .
R\D
. , , R^D . , /??D(CH) == 49 "1,
R (CH2) = 88 " 1 . H . , - -
182 MC-I, 417 "1. , TC() > -TC(OPTO,),
.
, /?f D . , . . . \ , .
,

, .
, -1
":
H3C-CH2-CH2-CH2(2)5CH2-OH
/?f, (V1) 0,32 0,45 0,64 0,91 1,21,3 1,54

, .
, .

-19 -13

413

*
1. Mooney E. F., An Introduction to 19F NMR Spectroscopy, Heyden-Sadtler,
London, 1970.
2. Roberts J. D., Caserio M., Basic Principles of Organic Chemistry, W. A. Benjamin, New York, 1965.
3. Spektrenkatalog, Bruker-Physik, Karlsruhe, Germany.
4. Technical Bulletin, Joel-Kontron Co., Munich, Germany.
5. Reich J. J., Jautelat M., Messe M. T., Weigert F. J., Roberts L D., J. Am.
Chem. Soc., 91, 7445 (1970).
6. Bremser W., Hill H. P. W., Freeman R., Messtechnik, 78, 14 (1971).
7. Ewers U., Dissertation, Cologne, 1975.
8. Gunther H., Jikeli G., Chem. Ber., 106, 1863 (1973).
9. Stothers J. B., Carbon-13 NMR Spectroscopy, Academic Press, New York,
1972.
10. Olah G. A., Mateescu G. P., J. Am. Chem. Soc., 92, 1430 (1970).
11. Emsley J. W., Feeney L, Sutcliffe L. H. (Editors), Progress in Nuclear
Magnetic Resonance Spectroscopy, Vol. 7, p. 52, Pergamon Press, Oxford, 1966.
12. Gunther H., Schmickler H., Pure Appl. Chem., 44, 807 (1975).
13. Breitmaier E., Spohn K. H., Tetrahedron, 29, 1145 (1973).
14. Clerc J. T., Pretsch E., Sternhell S., 1 3 C-Kernresonanzspektroskopie, Akademische Verlagsgesellschaft, Frankfurt/Main, 1973.

: 44, 5359.

) Mooney E. F., Winson P. H., Fluorine19 Nuclear Magnetic Resonance
Spectroscopy. In: E. F. Mooney (Editor), Annual Reports on NMR Spectroscopy, Vol. 1, Academic Press, New York. 1968; Jones K-, Mooney E. F.,
ibid., VoIs. 3, 4 and 5A.
) Emsley J. W., Phillips L, Fluorine Chemical Shifts. In: J. W. Emsley,
J. Feeney and L. H. Sutcliffe (Editors), Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 7, Pergamon Press, Oxford.
) Emsley J. W., Phillips L., Wray V., Fluorine Coupling Constants. In:
J. W. Emsley, J. Feeney and Sutcliffe L. H. (Editors), Progress in Nuclear
Magnetic Resonance Spectroscopy, Vol. 10, Pergamon Press, Oxford, 1966.
13
r) Pregosin P. S., Randall E. W. C-Nuclear-Resonance. In: F. C. Nachod and
I. J. Zuckerman (Editors), Determination of Organic Structures by Physical
Methods, Vol. 4, Academic Press, New York, 1971.
) Breitmaier E., Jung G., Voelter W., Pulse Fourier Transform 13C NMR
Spectroscopy. Angew. Chem., 83, 659 (1971). Angew. Chem. Int. Ed. Engl.,
10, 673 (1971).
) Gunther H., Physikalische Methoden in der Chemie: Kohlenstoff-13 NMRSpectroscopie, Chem. Unserer Zeit, 8, 45 and 84 (1974).
) Gray G. A. Carbon-13 Nuclear Magnetic Resonance Spectroscopy, Anal.
Chem., 47, 546A (1975).
s) Levy G. C., Carbon-13 Spin-Lattice Relaxation Studies and Their Application
to Organic Chemical Problems, Accouts. Chem. Res., 6, 161 (1973).
* . . .
. .

414

) Breitmaier E., Spohn K. H , Berger S., 13C Spin-Lattice Relaxation Times


and the Mobility of Organic Molecules in Solution, Angew. Chem., 87, 169
(1975); Angew. Chem. Int. Ed. E n g l , 14, 144 (1975).
) Mann B. E., Dynamic 13C NMR Spectroscopy. In: J. W. Emsley, J. Feeney
and L. H. Sutcliffe (Editors), Progress in Nuclear Magnetic Resonance
Spectroscopy, Vol. 11, Pergamon Press, Oxford. . 74.
13
) Shoolery J. N., Some Quantitative Applications of C NMR Spectroscopy.
In: C. P. Poole, H. Farach, Relaxation in Magnetic Resonance, Academic
Press, New York, Vol. 11, 1971. . 47.
13
M) Nelson G. L, Williams E. 4, Electronic Structure and C-NMR, Progr.
Phys. Org. Chem., 12, 229 (1976).
H) Hehre W. J., Taft R. W., Topsom R. D., Ab Initio Calculations of Charge
Distributions in Monosubstituted Bensenes and Meta and Para-Substituted
Fluorobensenes. Comparison with 1H, 13C and 19F Substituent Shifts, Progr.
Phys. Org. Chem, 12, 159 (1976).
o) Martin G. /., Martin M. L., pdot S., Theoretical and Empirical Calculations
of the Carbon Chemical Shift in Terms of Electronic Distribution in Molecules, Org. Magn. Resonance, 7, 2 (1975).

Xl

1.
. XI. 1. ,
. - ( 0,139 HM)
, ( ) -. . .

. XI. 1. (, [I]).

2.
-
H-H

,
1
UP H , . IV,
. X L l XL 2.

416

417

XI

. X J . 1

XI.1. (6-, . .)

1.58
2.75

C6H5-CH2-C6H5
.

.81

CH3

/H3
CH3

CH3

CH3

2,13

1,66

1,93

CH1

H3C'

0,97

O4

1.21
H H

1,81

.1,96

1,73

1,94

2)7

>

...

.CH3

2,46

2,65

2,55

CH3

6
2,37

2,66

2,2)

'22

0.86

1,51

1,54

0,93

2,57

2,60

1,963,03

2,22

2,230

COOR

3.53

2.02

3.59

H2C=CH-CHO

9.72
.

H2C=CH2

-CHO

9.53

10.0

-05 H^c^S;^H
I
5.16 H

I
H 6.26

7.06

6.03

5.60

^-

C6H5-NHCH3

2,44

2,32

1.25

2.92

2.20

5.29

NHCH3

1.84

2.00
H H

H3C-CHO
CH3

2.01

H 1.49

ft

'CH1

2.87
3.67

5 9

0> '

CH3

CH3

3.92

2.74

3,50

2,91

1,62

2,34

2,20

6.43

5,59

H
2,04

5.70

1,65

*
1

5.95

5.68

6.09

6.27

5.65

6.45

.69

1,85

5.79

6.28

6.25

6.76

|^>

4.53
7.71
6.10

4.70

14 X.

6.88
5.93

6.11 5.78
4.82
6.22

6.37

418

419

Xl
. Xl. 1

.
H

7.27

7.46

8.31 7.91

H3

/(1,2)

/(1,3)

2.-1)

/(3,5)

/(2,Si

/(2.3)

H
Cl
Br
1
NH2
CN

8,97
7,01
7,13
7,51
6,63
8,43
8,04
7,88
7,96

5,58
3,58
3,80
4,37
3,55
5,12
4,57
4,43
4,55

8,97
10; 26
10,16
9,89
9,65
9,18
9,26
9,19
8,76

8,97
10,58
10,45
9,97
9,89
9,49
9,66
9,99
9,60

5,58
7,14
7,01
6,63
6,18
7,08
7,59
6,94

4,34
-6,01
-6,12
5,94
4,29
4,72
4,00
-4,46
3,41

3
4
4
4
4
4
4
4
4

/(1,2)

/(1,3)

/(M)

/(1.6)

/(2,3)

/(2,4)

H
Li
CH3

7.54
6,73
7,64
7,86
7,93
8,05
8,05
8,02
8,40
8,55
8,36
8,17
8,30
8,36

,37
,54
,25
,35
,14
,12
,13
,11
,01

0,66
0,77
0,60
0,63
0,47
0,46
0,48
0,47
0,43
0,48
0,55
0,49
0,44
0,43

1,37
0,74
1,87
1,79
1,88

7,54
7,42
7,52
7,49
7,47
7,44
7,51
7,39
7,29
7,46
7,47
7,40
7,36
7,47

7.46
7.06

^6.6O

8.50

^Q" 7-40

7.04

8.00

7.19

6.62
H
7.70

7.82
7.33

7.47

7.09

^8.6O

8.50

COOH
COCl
COCH3

9.15

.2/

XI. 2. HH
()

7J4

Jf '

5'

H/
X

H
Li
COOH
CN
C6H5
CH3
OCH3

Cl
Br
F

'

11,6

19,1

2,5

19,3

23,9

10,2

17,2

7,1
1,7

11,75

17,92

0,91

11,48

18,59

1,08

10,02

16,81

2,08

7,0
1,3
7,1
4,65

14,1

-2,0

14,6

-1,4

15,2

-1,8

12,75

-3,2

2
2
2
2
2
2
2
2
2
2

Li

8,90

(C2Hs)3 Si

8,0
8,0

H
C6H5

7,62

CN
I
Br
CH3
Cl

7,60
7,33

N(C2H5),

7,13

OC2H5

6,97

*0(25)2

4,7

7,45
7,26
7,23

2
2
2
2
2
2
2
2
2
2
2
2

COOCH3

Br
Cl
NH2

N(CHa)2
+ N(CH3J3

NO2

OCH3

/(3,F)=0,22

14*

,CH 3 )= -0,75;

0,92

,18
,09
,03
,07

/(2,3) = 0,36;

2,1

2,27
2,53
2,76
3,05
2,40
2,71
2,94
2,74

/(3,CH3) = -0,62.

,37

1,29

1,51
1,31

,75
,78
,72
,60
,76
,69
,48
,74

1,76

1,82
/(1,F) = 8,91;

5
6

7
8
8
8
8
9
9
9
9
9
9
8
/(2, F) = 5.69;

420

XI
. Xl. 2

. XI. 2

H H

S(J)
[10]
Cl

Br

NO2

+0,61

+0,53

+0,39

+0,77

+0,79

0,34

0,23

0,27

0,25

0,20

0,32

14

0,24

0,16

0,20

0,19

-0,16

15

+ 1,21
-0,04

+0,87

+0,71

+0,51

+ 1,02

+1,33 I

+0,03

0,05

0,04

0,07

0,16

+0,39

+0,34

+0,36

+0,37

+0,08

+0,38

Ns=VH '

2 ,

"

8,9

7(1,3) + 1,48
+ /(1,4)

/(1.5)
7(1,6)

8,75

10,14

1,50

Mo(COh

0,22

0,72

0,54

/(2,5)

0,69

0,76

/(1,7) )
/(1,7') J
/(2,7)

7(2,7') i

6,7
0,4

10,96

6,97

6,81

0,73

0,77

0,51

0,34

8,45

8,43

3,17

2,75

8,90

8,70

0,57

5,89

6,47

1,42

0,74

4,45

3,1

7.15

5,65

1
H

5,5

< 0,4

15

2,0

16

Y N

6,3

3,8

7(1,2)

/(1,3)

/(1,4)

-13,05

3,65

13,12

H1
2

/^~^~
^^~"~~~~J~H*

/(2,3)

2,96

H'
H'
'

/(1.2)

Jx Vr
H

H1

1.

H2

7(1,3)
1,75

1,32

0,92

0,94

*3'

<1'2)
2,85

/(1,3)

/(1,4)

/(3,3')

0,35

1,0

12,00

7(1.2)

/(1,3)

/(1,4)

/(2,3)

/(3,4)

/(3,4')

4,65

1,75

Hf
> 5
5

1,07

H*

V^H*1
JL-^H3

3^*Y^H '
H*

5,05

1,09

/(1,5)

/(2,5)

1,98 1,91 1,33

1,51

H1'

H3

xW

w-2>

7(1,3)

9,64

1,02

1,12

Al^)
10,2

/0.3)
1,9

/(1,4)
0,1

/(1,4)

/(2,3)

5,04

H*

/(3,7)

0,32

/(7,7')

13,0

14,05

14,14

11

12

13

14

11

iAi
,IMJ4

:JJ

H2

5,51

I
H

1,38

/(2,3)

11,17

1,27

8,4

0,25

/(2,4)

/(3,4)

8,2

5,59

/5

Cr(CO) 3

7(1.2)

*(2/ - - Gh'
( <Gr
> '
(

|
3

'

-0,22

2 _

31

+0,81

\\

13

OCH3

12

23
24

421

R' V

/(2,41
3,0

()

XI

422

. XI. 2

"

3
3

3. (V.3)

/(1.2) /(1.3) 7(1.4) /(2,3) /(2,4)


9,76
0,90
0,88
5,78
1,80
/(1.2) 7(1,3) /(1.4) /(1,5)
1,74
10,17 0,86 0,60
/(2,3) /(2,4) /(2,5)
17,05 0,83 0,60

/(1,6)
1,30
/(3,4)
10,41

7(1.2) /(1,3) /(1,4)


7,54
1,37
0,66

/(2,3)
7,54

/(3,4)
9,45

21

423

(. XI. 2):
= sin 6 cos , = sin 0 sin , Z = TCOS
(V. 3)
_
1
_ ( ft

2
SV = * s i n G \

22

~"~ 2

(XI. 1)

smQ

F*
0 = 90.

8,28

1,24

0,74

6,85

23

8,55

1,20

0,82

6,59

23

6,87

0,82

1,04

8,34

24

. XI. 2. .

1,75

0,85

1,4

3,3

25


(XI. 1) (V. 4).
4.
: Q .
Q
(ym = qmym
( X I -2)
. , a qm . <i|>n|$<3|i|>m> :

5,00

1,06

2,80

3,50

26

R \ Pm)

4,88
1,24
/(1,5) /(2,4)
0,13 1,97

X
/(1,2)
CH2
87

"8,77
NH
8,82

1.00

7,67

/(1,3) /(1,4) /(2,3)


0,02 4 6 9 , 1 9 28
0,28 1,13 9,28 28
O1OS 1,50
9,31 29

27

( XL3)

<3 ,
(Tm | RQ I1Fn)=H1Pn I QR I ^m)
R. <5 , , *
< 0 | $ | ) = (0|) <0| Q I X) = (Q^I ,)

(XI. 4)
(X I. 5)

(XI. 4) ,
(XI. 6)

* , , ( ).

424

, (1/4)/.
E2 E3

(XI. 3) (XI. 4)
|| ^m)
(XI. 7)

\) = 0

<?
qm , <Y| \
. , , . 4.3.3 . V.

(1/2) V A -

/AB/V2"

/AB/V2~

-(1/2) v A + v B -(1/2)/ -

('- // (J).
?,
m/ (i) (. 2.1 . I I ) :

'AB/V2"

(XI. 11)

V A -

(XI. 12)

(XI. 8)

(I)

I2
,

yV

z=ZM<)
(XL 9)
i
/, Fx
?. , ,
<0*|5#|0/> , 0* / , . . F2.
6. AB2
. V. 2, 02 03, 04 05
, , . . ,
. 4.6 . V. , 2
H13 ^(\\ 3) = ( ( + pa)/V2~| \ ) =
| 2 \ ) + ( | \ ) )

-v

(XI. 13)

-/AB-

S = Y ^ B - T A B * ! / ~*) + ( A V

=2
45 = 4.
2- (. 4.1 4.3.1 . V ),

0(A) 0(B) EA BB.
,
H =E (1/2) V A + V B + (1/2) /
5 = - (1/2) V A
"-

, AB 2 (. . V. 7) , !
:
f, = EI- E3^-~(vA + V B ) + -|/AB + O+

=V

I1 = ~

B C+ + _

fs = E5- B 6 = (V A + v B ) - | /AB - -

66 =* E 6
H11-E1 : (1/2) V A - (8/4) /

=. E0

- (1/2) V A -(3/4)/

'AB +

/ AB C+

(I/V2") [(1/2) / + (1/2) /] - /AB/V2~

11

(XI. 10)

=0

(1/2) V A - V B - 0 / 2 ) / ,

5. F,

mi

425

Xt

__

__

Og

I; m U]S 'g !

:;ro SOD i

g"-

J.OISWH g KITOU HXHanouwoH 'woEBdgo WHHBX '(l ' ' 1 ' ) ^'* HXOOHOOITU a
-adxo ou m KOX9BtnBda 'g airou 'XBHHVdooH HWBXOHO
oxdeH3V-z 4iroVa oHairaBduBH g airojj -'g BITOU KoojanioiBnreda g BITOU
OJOHXHHJBW ojoM03hHXBio BoiaeaHVBifMO g au-ou dWK g

(H 'IX)
-JBW a

! g -ou WOHIHH
BiHawow OJOHXHHJBW aHHaVaaou 'HHdoax OHOBITJO;}

VXOLT9 3HH3H8VdA '8

-^

sI ^!

BJ

I 1= 3

I q= v 3

} =

:
-HIT 1 aoifBedaxHH KVV aHteoiXiraifo 1 - BL-Jf
'(6I ' '1 ') HanaodA XHHoahHX3Jd3H6 awwEdjEHV BH WBfoxadsu WNH4b-atr
-xo - xHH4ifBXHawHdauoMe EHITBHB aHHXHBdu BJ-J
edxMauo BdxHali - BOXOIBV -V . q 'v HHHHIT ^,
3

W - id - P)A = M - z( ~ )A = 7

~> " "To"to to"to tow"coco WV"cn"o)"o>Vj ""

"

"~

23

OOOOOO

888;838.;888.888

I IIl II Il I I I I I I III I II II

*-

| 2

P>2??>P>o>OTcn*..^j^*.*..tv,ii.*.eocococogtog ^- Og
""">)" "cnVj^co'to ^'''.-
""
)"* -lCnoO)tOO)-*J '^cO ^ "**^''OO
fc

:k

"

*W ^

I II I II II II II II

) **! **! ^J 1^J *^J "1^ *-J "*^ OO OO OO OO OO OO

^Jk >w ' pi ' Jc Jo Jo jo1" -*1J3 ^ ^w ^w ^w Jo


^^^^>>11^%-!^-^- CO Oo Os Cn "^ "^-*

It'

--
^

W^J^J^J^J^J^J^J^J^^J^^J^^J^J^J^JOJOJoJSjOJOJOJOJO
" " oo'ooVjViViVjVi'cn'cTj'oi'oJOi'bi W to -t-

5I

"

^
*
2
&

Ii
i

-axBgBHoV eag 4oaffe HSBV wndoxoH '


8I4HH3V33HdU

BOXMXE4ITOUOH ,gg^V

BEHITBHB

OJOWBdU

[ 0] <aaVCMLTVHV OJOWKdU KLfV iqi/AWdOCD 'L


' aodxHSUo
-BX3dud3XHH Hdu HWHHESITOU xXjow BHHHBV HXg 'g 'IX 'irgex a NHaVaandu
QOjv/BVy XHHhHITEBd BITV 1 RXOXOBf 1 '9 0 A^V/

- 1 HwaxoHO BdiMauo VHB ' HB^J


BoxaBandiBwooBd 4oaVe -
-11 ' - - 'ITJ j'g'g "VEBd
-ndu ' BSHITBHE ojowBdu BHHaHSBdX xoiXtfairo YHJ.S [%

(jp )

~_s

- - - . , , I ~J -J OO OO OO OO OO OO OO OO 0000 OO OO " CD
~ i o o o O " C o o o c o c o o o " tococo^cnaicocooto^oooo

7( 4

Ir

"" "to "to "to "to ' " "*. V ' > Vj Vj " " "

q I v

X B
B

I ) tO -sj tO"4"tO tO"n- O O'cO OO ~-J Vl "O) "*."*. " "( "to "OO
I OO 00^- *. ~J O > ) ) >t-OO >

'"~

-HOHliBdaiH owtnowoii oow waxee andoiOH ' 1


adsw
HaHHBdH ou KITV XHHHBV xnuqifBiHawndauoMS OHhoxBiooV
-Au-OU 1 OMBHVo '3BhXiTo waTngo g 'Bdxxauo -, -,VV
-adau BDiaefoiifgBH ediaauo adiHaft 'BiinsHVXdXBe
'aofoxadau XIVoda OJOHW ^ BOiaawn -

.-

^-'^"''"* "''' "' rf*.4^."rf*. > Ci^

I IIIIIIII

^5 ( < ^ ht. ^> ^> ~^1 OO ^ Q) ) "4I

L\ I I I I I I I I I I I I I I I I I I I I I I I I
8

>,,-1 C n * . t O t O t O t O t O t O t O t O t O t O tO JO to JO JOJOJO JO JOJO JO


tn"> "o>" V)Vj"o)"ai"cnV V"co"co"to"to"> tt-"
> OO OO to O)O *. OO OO OO tO CD > *>. tO> OO
8>" 1">> " " -

I
**

""

428

Xt

(Xl.14)
:
dMxldt = (MyB0 + M2B1 sin <o<)
dMy/dt = Y (M2Bi cos wt MxB0)
dM2/dt = Y ( MxBi sin wt MyB} cos wt)

(XI. 15a)
(XI. 156)
(XI. 15)

Mx :

JVlv

- -

..
My =
2

Y (MyB0 + M2Bi sin at)


Y (M2B1 cos at MxB0) My/T2
Y ( MxBi sin wt MyB\ cos wt) -

',
;
Mx = , cos wt Mx, sin ait;

My

(XI. 16a)
(XI. 166)
(XI. 16)
-

My, sin wt Mx, cos wt

dMx,/dt = - (W0 - ) , - ,/2

(XI. 17)

dMy,/dt = (0 - ) Mx, - YB1^2 - ,/2

(XI. 176)

dMJdt = YB 1 Al,, - (Mz -

(XI. 17)

AIo ,
.

(. . )
Mz, Mx, , . (XI. 17) :

O0 -)
|(0 -)2


, , , .
(XI. 17) (XI. 176) ,/- G:

, M2

2/.
|(
0- /

( Bi),

dG/dt = i (0 ) G /Y

(XI. 18)
(XI. 186)

dGA/dt

a A G A = - JY

dGB/dt

aBGB

(1/T2) G

(XI. 2Ia)
(XI. 216)

(XI. 18)

(XI. 18) (VII. 4),


. KO-

(XI. 22)

(XI. 226)

. = 1/T2/! i'(coo ) = 1/2 i(co0 ).


, (/- .
, (XI. 22)
:
GB/TB - G A /T A

dGA/dt + a A G A = - /Y

(XI. 23a)
(XI. 236)

dGB/dt + a B G B = - /Y

I/TA = 1/ = &
() .

, . . dGA/dt = dGe/dt = . M0A = ^
MOB = PB = AIo, PA ; ,

AI0

(XI. 20)

G = Mx, + 1,

,=

(XI. 19a)

9. ,
[35, 36]

[AXB] - (AyB2 - 4,B,,)/ + (AxBx - AxB2) ] + ( - AyBx) k

dMx/dt
dMy/dt
dMjJdt

7*2 (0 w) 2, cos ait + 2B1 sin /


1 + T ^(CO 0 -) + Y B T 1 T 2

ri2
2
2
2---

2Bi cos ait T 2 (CO0 ) 2Bi sin wt


-5 5-55- (XI. 196)
1 + Tl(CO0 -co)2 + Y 2 S 2 ^ 1 T 2

i, J K k .
, ,
.
(XI. 15). T2 , ,
z TI.
,

429

{1

+)(1+)-1

.v
o
L 24)
T

, (/-. , , (XI. 20),


, .
,

XI

430

431

(XI. 24) .
(VIII. 2), ( = 2nv)
( V A + VB)/2. ,
, I/TZA \\.
, ,
,
. MJ, 2 ,

(, + + kia) GI &2iG 2 It3]G3 = /YBi


+ (2 + 21 + 23) G2 kS2G3 = i\Bi
U 23 G 2 + (O3 + ftsi + 32) G 3 = Iy

(XI. 25a)
(XI. 256)
(XI. 2)

:
AG = - J C P

(XI. 26)

, ( = \BiMo), a P G .
~',
G = -/CA-1P

(XI. 27)

GI, , !/- GT, (XI. 27) - I


G T = IG = - 1 ~ '

(XI. 28)

(XI. 28) . . (. .
) (XI. 28)
= / C [ I , 1, I ] A

fl]
L

JIz

"8- _

,
= 2/ (7v ^) + nS + X

(XI. 29)

S
S

I ; v (); W
Vj (); ()
X

*</'

, , *.
* , .

CU

432

433

XI
10. 13C

. . XI. 4 XI. 6 . XI. 3 XI. 4.

XI. 4.
[39]

13

C 6

TMO - -

|
,

_ -
ft-

()

\
\

220

200

led

. XJ. 4.

' wo ..

26,06
29,22
39,56
53,61

27,51
30,43
40,48
54,02
67,40
77,17

95,99
128,53
178,27
192,8
193,7

76,91

127,96
"*

TMC , 6 = 0,0 . .

Xl. 5.
[39]

13

C ,

13

C [38].

11.
( MKCA)

()

().
(MKCA), (),
*. 1973 .
.
. XI. 7, , .
,
H
7
4-10~ , (' / 2 -- 1 ).
, ,
. 5, H ( = ),
. .
- / / (I =
= 4,18 ).
* 1960 . XI

SI (
Systeme International). . .


1,4-

27,5
27,4
27,8
27,6
27,3
27,0
26,8
27,3

128,5
128,8
128,3
129,0
128,8
128,4
128,0
128,5

193,0
193,3
192,8
193,4
193,2
192,6
192,4
192,5

TMC ( 20 . %).
13

Xl. 6. 6( C) (. .) [4050]

2,3
5,7
15,4
3,0
13,7
13,9
13,9

^
15,9
24,8
22,6
22,9
23,0

~~
34,5
32,0

32,4

29,5

434

XI

435

. Xl. 6

. Xl. 6


C3

-2,6
23,3
26,5
27,8
29,4
27,8
27,0
26,2

3
4
5
6
7
8
9
10

38,7

*
1^30,1

128,8
125,4 114,7
126,5
145,2
122,1
125,8
143,3
124,0
125,2
136,4
128,8
1257
1 7
1 9 7
126,0
140,6
128,7

3
4
5
6

^3^26,0

-?

GI

C2

Br"
Cl"
F-

123,3
COOEt
853 1304
OCH3
115,5
122,0
OCOCH3
CH2=CH126,0
117,3

-C=

108,9
137,2
130,2
126,9
132,1

3
4
5
6
7

129,7
130,4
1532
841
141,6
96,3
136,9
116,3

*4?

O=CH2

P=CH2

V=CH2

2,3
31,4
32.3
25,1
29,0

22,7
22,6
27,3

"
^

257

124,6 ^ 5 8 J l 22 3
^*^

126.1

25,2
23,3 28,2
25,8

HCIsCZ-X

Ol

71,9

-C4H9

66,0 83,0

^L

12,

"f 4
^

77,7
81,4

126,1
126

@811u

IPl

^ 128,1

IMJ
124,9

131

128,3

134,1 ^^25,8

Ci

-C6H5
71,9
-SCH2CH3

32,0

130,0 123,0

126,7

^151,9^

140,1
135,2/ ,37,4

i 128,8

i
,-14

10

18,4
29,5
32,7
29,3
36,6
32,1

124,1 " L J l

HGIe=QZ-X

133,9

4 3,4

Y-CH 2

32,6
32.1

75,4

48

P-CH2

C2

0-CH2

w
128,9

Op^
127,3
^xSv

132,3

^O

V=4s^l23,9
119 7

'

137,4

C2

83,3
72,6

. XI. 6

= 128,5 +

H
-CH3
-CH2CH3

-
( 3 )

-CH2Cl
-CH2Br
-CF3
-CH2OH
-CH=CH2
-C=CH
-C6H5
-F
-Cl
-Br

Sl (1)

S1 (60)

0,0
9,3

0,0
0,6

15,7
20,1
22,1

0,6
2,0
3,4

15,1

-3,3

9,1
9,2
2,6
13,0

0,0
0,1
2,2
1,4

7,6

-1,8

6,1
13,0

3,8
-1,1

35,1
6,4

14,3
0,2

5,4
32,3

3,3
9,9

Sl (*)

Sl ()

0,0

0,0

0,0

3,1
2,8
2,5

0,1
0,0
0,4
0,6

0,2
0,4
0,3
0,0
-1,8

0,5
0,9

1,0
4,4

1,0
2,2
2,6

1,0
0,4

26,9
30,2

-12,7

1,4

7,3

14,7

0,9

8,1

19,2
22,4

12,4

1,3

15,7

0,8

19,3
19,6

4,4

0,6

9,5
11,8
5,9

-5,3

0,8

-N(CHs)2
-N(C6H5),
-NO2
-CN
-NCO

0,3
3,2

0,4

Sl (0)

OCH3
-NH 2

-3,1
3,6
0,2

1,2
3,5
0,2

Sl (1)

-2,0

16,0
5,7

Sl (UM)

3,5
3,6

0,7

6,0
4,3

1,2

2,8

-SC(CHa)3

-COCH3
-COOH
-COO"

4,5
90

9,0

1 2

1 9

9,3
2,4
7,6

0,2

0,2

1,6

0,1
0,0

-COOCH3
-COCl

2,1
4,6

0,8
1,2
2,9

Sl ()

-0,3

0,0
0,6

0,0
4,2
48
2,8
44
7,0

. XI. 6

C

Cn

, N CH3
, N CH3

39,5
72,6
68,4
69,8
67,4
28,5
57,7
56,7
47,9

22,9
26,5
27,0
17,5
24,4
27,8

128,7
128,3 I 136,0

24,2

25,9

N^YN^
4 I

> 147,9

152,0 Us N AN'
"

153,1

129,0

128,4

* H

154,9

130,3

136,0
126,8 12

127,9

149,0

18,7
27,5
143,0
118,7
124,9
149,9
141,9
139,1


--

W3
8
126JB(^Np*S|ia,5 130,5 (^y ^ >
29.7 S8x^k.,S 150,9 127,5 ^Jfv^^N

13OJ ]

135,0
163,7

UW 125,3
121,1

^8'6
iW

^ 135,2

119,2 | ^
Os
1
141,2
128,5
126,6 1 124,2

5
1 136,6
1 N^
^ 147,8 '129,4 ^5^^^
IT
N^j
4
I^ J 152,4 128,8
T
kJf^ V 0
159P^J | "
124,7 1 1355

152,4

129,4

29,7
109,9
107,7
126,4
123,8
128,5
126,4

136,0
148,6
126,4

438

XI
,
. , .

X l . 7.

/,

m
t

2
2
2
-

10
3
10

107
7
10 ; 0,239

-- - -

--1

--1

V-

- - 2
-2
103

X
!" 4 X
1
-XT- X
- 1 - -1

Xc- 1
2
2
2
H - A - -- -

2.
2.1. () ,
, .
H 2.2. ;
,
,
, , .
, 2. , ,
, ,
.

2.3.
,
. - , "
,
.
, 2.5.

,
.
.
.
2.6. ,

, ,
,
.
2.7.

.
() , 2.4. V 0 () (. . 2.9).
,
2.7.1. ()
,
. ,
, (. 1), .
2.7.2. ()
,
(T) ( I T =
= 104 ).
2.4. !. .
2.8.


, :

/.
Vo=^o
Y
.
(. 2). 2.8.1.
- ,
Hi.


,

, .
,
1.

,

2,9979 10

10~

4
10 ()

4 -1(T3
()

12. ,
,

()
*
1.
1.1. , . * E 386
E-13
(ASTM). 26 1976 ., 1976 . E 386-69.
E 386-74.

440

( , ,
).
2.8.2.
,
, . .
.

,
.
,
.

2.8.3.
,

, .
2.8.4.
,
, .
2.9. 8.

VK ,

,
,
Av
,
, . Av
,
.
2.9.1.
(
),

2.9.2.

, ( )
( ) .
2.10. () , -

, (
),
, .
,
, .
2.11. () ,

, . ,
. ,
.
2.12. MP ,
(), .
2.13.
-
() J -

, ().
. */
. , , ,
3
/( 1 5 NH).

3.

441

3.1. , ,
/
/ .
3.1.1.
,

,


, .
3.2.
, , , ,
, , .
3.2.1. - .
,

,
(), .
3.2.1.1.

-
,

.
3.2.1.2. -

-,


.
3.2.2.

,
,

,

.
3.2.3.
,
,

-

,
.
4. ,
4.1.1. (
)

,
.
4.1.2.


( , . . 4.1.4)

,
.
4.1.3. /,
.

/
/ :
Av

2
4.1.4. ,
, , . ,
.
4.1.5.

, ,
1
, , , H TMC
.
,
.
4.1.6.

()

442

XI

,
, () .
4.2. ,

:
4.2.1. (v)
(, ),
.
4.2.2. () ,
.
4.2.3.
.
4.2.4.
( ),

(, 90-, /2-).
4.2.5. HI ( ).
.
,
.3.2.
4.2.6. , *.
. , 900^.

2. , , ,

, .
4.2.10. ,

(sampling
rale) , .
4.2.11.

.
4.2.11.1.

, .


.
. sampling time

.
.

4.2.7.
() , .
4.2.8. , (homospoil pulse) H.
4.2.9. ,
(),
3 (50 %).
1.

.

4.2.12.
.
4.2.12.1. ,
.
4.2.12.2. ,

,
90.
4.2.13.
, . (
, ).
4.2.14.

, ) )

.

* . : . : .
. M.: , 1963.

. .
. .

(/2) ^.

4.2.15.
,


.
4.2.16.
,
.
. ,
, ,
. 4.1.5.
4.2.17.
.
. , , (90, T) n
,
(90, ).
4.2.18. .
4.2.19.

.
.

.
4.2.20.
.
4.2.21.

() .

. , .
4.2.22. , .
4.2.23.
,
. -

443

,
.
4.2.24.
,

, (180, , 90), .
4.2.25.
, . ,
(90, , , , 90, T, , ) (90) ,
, 90 T, (90)
90-.
4.2.26. 90, (, 90) ,
,

(,
).
4.2.27. --
90,
t,
180.
4.2.28.

90, , 180, (2, 180),
.
4.2.29. 2 180-
.
4.2.30. (CPMG-)
9Ox, ,
180, (2, 180).
4.2.31.

90^
(SL),,, SL
( ,
) Hl > ().
4.2.32.

.

444

4.2.33. -
,

- .
4.2.34.
() (. . 4.1.6) , ,
,
.

,
.
5. ,

XI

5.1. -. :
= 5,00 5,00. ,
= 5,00 . . =
= 5,006, .
5.2. .
5.3.
.
5.4. (
).
5.5.
,
( )
.
5.6. .

6.1.3 , 13C
1 H, ,

, , .
6.2. .
6.2.1.
(TMC) 1%.
6.2.2.
.
6.2.3.

2,2,3,3--4,4-4- (-).
.
6.2.4.
( )
TMC .
6.3.

, .
6.3.1. ,

( ), . ,
,

.

6. ,

. ,
,
.

.

13C.

.

6.1. .
6.1.1. , 1 13 ,
H C .
6.1.2. .

6.3.2.
13
C (TMC).
,
, , .
,
-

TMC
.
6.3.3.

10
11
( B B)

(C 2 H 5 ) 2 0:BF 3 .
6.3.4.

31
P

(P 4 O 6 ).
6.3.5 ,
.

.
, ,
.
,
.
. ,

( ),
. ,
,

.
7.

7.1. .
,
:
7.1.1. .
, , , 14N, 11B. , , "F,

445

7.1.6. , .
7.1.7.
(. . 2.4)
,
( ) , .
7.1.8. ,
.
,

,
:
( ), ,
, ,

.
7.1.9. ,
.

(
,
).
7.2. , , :
7.2.1. .
7.2.2. , .
7.2.3. - , ,
.
(. .),
().
7.3.

- :
7.3.1. .
7.3.2. 90-
.

31

7.1.2
.
7.1.3.
, .
7.1.4. .
7.1.5. .

.
. 7.3.1 . 7.3.2.
, ,
90-
.

7.3.3. (

446

XI

). (. . 4.2.9)
.
7.3.4. (
, ).
7.3.5.
,
.
7.3.6. , :
)
; ) ; )
; ) ;
) ; ) , .
7.3.7. , .

7.3.8. , -.
, .
7.3.9. ( ), .
7.3.10.
.
7.3.11.
,
, ,
. .
7.3.12. , .
7.3.13. .

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

10.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.

Heigh C. W., R. ., Org. Magn. Res., 4, 203 (1972).


Bothner-By A. . . 72, . 1.
Watts V. S., Goldstein J. H., Chem. Phys., 46, 4165 (1967).
Grecely V. S., Watt V. S., Goldstein J. H., J. MoI. Spectr., 30, 184 (1969).
Read J. M., Mayo R. E., Goldstein J. H., J. MoI. Spectr., 22, 419 (1967).
Castellano S., personal communication.
Williamson M. P., Kostelnlk R., Castellano S., J. Chem. Phys., 49, 2218
(1968).
Castellano S., Kostelnlk R., Sun C., Tetrahedron Lett., 4636 (1967).
Castellano S., Sun C., Kostelnlk R., Tetrahedron Lett., 5207 (1967).
Read J. M., Crecely R. W., Butler R. S., Loemker J. E., Goldstein J. H.,
Tetrahedron Lett., 1215 (1968).
Qunther H., Wenzl R., Z. Naturforschg., 22B, 389 (1967).
Gunther H., Qorlltz M., Hlnrlchs H.-H., Tetrahedron, 24, 5665 (1968).
Gorlitz M., Dissertation, University of Cologne, 1969.
Gunther H., Wenzl R., Qrimme W., J. Am. Chem. Soc., 91, 3808 (1969).
Mortimer F. S,, J. MoI. Spectr., 5, 199 (1962).
Garbisch E., Griffith M. G., J. Am. Chem. Soc., 90, 6543 (1968).
Lambert J. B., Jovanovlch A. P., Oliver W. L, J. Chem. Phys., 74, 2221
(1970).
Hill E. A., Roberts J. D., J. Am. Chem. Soc., 89, 2047 (1967).
Copper M. A., Blleman D. D., Pearce C. D., Manatt S. L., J. Chem. Phys.,
53, 2343 (1970).
Regel W., v. Philllpsborn W., HeIv. Chim. Acta, 52, 1354 (1969).
Regel W., v. Phtllptborn W., HeIv. Chim. Acta, 61, 867 (1968).
Hobgood R. T., Goldstein J. H., J. MoI. Spectr., 12, 76 (1964).
Pawliczth 3. B1, Gunther H., Tetrahedron, 26, 1755 (1970).
Fraenkel 0., Asahl Y., Mitchell M. J., Cavu M. P., Tetrahedron, 20, 1179
(1964).
Read J. M., Mathis G. T., Goldstein J. H., Spectrochim. Acta, 21, 85 (1965).
Garbisch E., J. Chem. Educ., 45, 492 (1968).

* .
.

27.
28.
29.
30.
31.
32.
33.
34.
35.

447

Castellano S.. Sun ., Kostelnik R., J. Chem. Phys., 46, 327 (1967).
Gunther ., Z. Naturforsch., 2Ob, 948 (1965).
Gunther H., Hinrichs H.-H., Tetrahedron, 24, 7033 (1968).
Dischler ., Maier W., Z. Naturforsch., 16a, 318 (1961).
Dischler ., Englert G., Z. Naturforsch., 16a, 1180 (1961).
Dischler ., Z. Naturforsch., 2Oa, 888 (1965).
Gunther ., Angew. Chemie 84, 907 (1972.
6, 11.
6, 11; Binsch G., In: Topics in Stereochemistry, Allinger N. L. and
Eliel E. L. (Eds.), vol. 3, Interscience Publ., New York, 1968.
36. Sack R. A., MoI. Phys., 1, 163 (1958).
37. Bremser W., Chemiker Ztg., 97, 248 (1973).
38. 57.
39. Levy G. C., Cargiolli L D., J. Magn. Res., 6, 143 (1972).
40. 58.
41. 57.
42. 56.
43. Grant D. M., Paul E. C., J. Am. Chem. Soc., 86, 2984 (1964).
44. Burke J. J., Lauterbur P. C., J. Am. Chem. Soc., 86, 1870 (1964).
45. Maciel G. E., J. Phys. Chem., 69, 1947 (1965).
46. Grutzner J. B., Jauielat M., Dence J. B., Smith !. A., Roberts J. D., J. Phys.
Chem., 92, 7107 (1970).
47. Dorman D. E., Jautelat M., Roberts 1. D., J. Org. Chem., 36, 275 (1971).
48. Gunther H., Jlkell G., Chem. Ber., 106, 1863 (1973).
49. Gunther H., Jikeli G., Schmikler H., Prestien J., Angew. Chem., 85, 826
(1973); Angew. Chem. Int. Ed., 17, 762 (1973).
. Stothers J. B., Can. J. Chem., 53, 581 (1975).

11.1. AnC 28,8 :64,4.


14,4 : 21,47
1 : 1,491.
11.2. . , . . 1, 67,27, 65,30
62,17 , .

1 0 : 9 : 6 40, 36 24 . % .
II. 3. : : = 38,6 : 48,6 : 12,8.
11.4. 4,78 . . 286,8 60 .
. II. 1 , .
11.5. ) ~60,9, 3,5, 7,2 ( 9 : 2 : 5 ) ; ') ~61,2, 2,2, 3,5, 7,2 ( 6 : 3 : 3 : 4 ) ;
) ~60,9, 2,0 (3 : 1); ') ~60,9, 2,7,3,0 (9: 1 :2).
II. 6. ) 1,2-; ) 1,3,5-; ) 1,2-;
) 1,2;5,6-/; ) ; ) 2,5-;
) ; ) 1,2,4,5-;
") 9,10-; ) .
II. 7. 1) 1 : 1; 6 1 : 3 : 3 : 1 . 2) / = , . / > 1 : 2 : 1 , 10
1 : 9 : 3 6 : 8 4 : 1 3 6 : 8 4 : 3 6 : 9 : 1 . 3) 1 : 1 ; 6 (1 : 3 : 3 : 1)
( 1 : 2 : 1 ) ; ( 1 : 1 ) ; d ; 4) 1:1 1 : 1 ; 1 : 1 1 : 3 : 3 : 1 ,
1 : 3 : 3 : 1 ; , b; d 1 : 1 1 : 1 . 5) 1 : 1 ; 1 : 6 : 15 : 20 : 15 : 6 : 1;
1 : 3 : 3 : 1 ; d 1 : 2 : 1 . 6) 1 : 1 : 1 ; 1 : 1 .
11.8. a) AMX: /AM = 4, / = 2 / <
; 6) AM2X: / == 1,
/AX = 5 / = ; ) AM 2 X: / = 3, /
4, /MX = 1 ) AMX3:
/AM =

5, /AX =

2, /MX =

1 .

11.9. ) Na[10BH4] Na[11BH4]; ) C 6 H 6 CHD 2 ; ) 1 5 NHj; ) "NH4+ .


. I. 1.
11.10. 1)
; CeHsCH2SH;
;
CH3CH (NO2) COO2H5.
2) 6- 1 = 4,2 ; ,
1 = 2,1 . (6 7,1) 6,3
14,7 , - -
. , . 147 6,3 64,7
6 4,4. , , - -
. , 1,5 .
3)
50 .
, - 15 6,6 . - -

449

15, 7,8 1,5 . , ,


, [
3
3
/(, H) /(CHsH)]. 3
, [ /(, H),
(H, CHO) V(CH 3 H)].
II. U. 6() 7,36; 6(6) 8,77 . .; = 5,0 ; Jac = 1,5 .
II. 12. . Gunther H., Gorlitz M., Meisenheimer H., Organic Magnetic Resonance, 6, 388 (1974).
IV. 1. ) 7,06; 6,7,27, 6 7,08; 607,81; 6*7,91; 6 9,30. 12,7 60 7,02; 6. 7,27; 6 7,04.
6 .
IV. 2. ) .

a- COCH3,
^- . -^-

.
) ( ) -
-, -
.
) CN .
- tjuc-
CN.
IV.3.
H (4) H (9)
, , . , 0 = 90, (IV. 5)
: Aa == /12/?3.
AX = 630 10~36
3 /

AX =
= 16,67/3 . ., R ( H M ) .

.
0,140 HM, H 0,110 HM
120, :
(4):

= 0,348-10" 8 HM = - 0,40 . .
= 0,366 ~8 HM

9):

R0 = 0,475- 10~

= 0,34 . .

= 0,16 . .

= 0,348 10~ HM = 0,40 . .


Aa(4) = 0,74 Aa (9) = 0,56,
- 8,01 (H4) 7,83 (Hg) (67,27).
6(H 4 ) 8,93 6(Hg) 7,71. ,
4 .
, (4) (5).
IV. 4.
Ap1-:

A p i = + 0,413
Ap 2 = 0,053
3 = _ 0,077

Ap 4 = - 0,152

15 X.

450

Hp

. Jca,
Jca , 1- ,
- : ] = 11 , he = Jed =
= 6 . -
,
.
IV. 6. ,- ?- 7 : 3 .
- : 3 / =19,6 ; 3 / =14,2 ;
3
/(, 2 ) = 6,5 ; 3/ (H, CH 2 ) = 8,0 ; I 4 J(H, CH 2 ),\ = 1,4
| V (H, CH 2 ) | = 1.2 . - - CH2 . - -
, -, - (. 60 . 2.3.2 . I V ) . 3 J ( H , CHi) rpawc-, .. . -
V(H 1 CH 2 ) ,
.
IV. 7. , -. 716 .
H 2 - C ( I ) (6).

- .
IV. 8. 13,1 Jaa . 72.
IV. 9. 74
-, 4 / -.
2 6.
IV. 10.
77.
V. 1. ) ''; ) ''; ) ABC; ) A 3 B; ) A 6 X; ) AA'MM'XY;
) ''; ) ''; ) A 3 B 2 X; ) A 2 X 6 ; ) ABCD; ) ABC 2 ; ) A3KHX,

H Y

Ri=R5 = 0,341 HM; 9, = 95 = 2044'

Ri
R2 = K4 = 0,217 HM; 92 = 9 4 = 3353' R2 = #
R3 = 0,110 HM; G3 = 0
# = /?5
#6 = 0,390 HM; 66 = 0
R4

= 0,390 HM; 9, = 0
= 0,314 HM; 6; = 66 = 2044'
= 0,217 HM; O 3 = 5 = 3353'

= 0,110 HM; 84 = 0

, (IV. 15) :

"" V 1 1,62 '" '

0,077
I 04^
U
11,62

0,153
4,71

0,077
11,62

iu

,j

0,053 N
15,21 )
0,052
15,21

21

0,00

4,7

17

V)

' 0,413
(
, 11,62
Q^

4,71
0,053

4,7 1

0,077
1,21

1,06 . .

= 2,01 . .
: ^=1,07 . . =1,22 . . ^-, , . , .
, ,
. ,
(Ax = 91-1O -3 3
), .
.
[., , Castellano S.,
Qunther H., Ebersole S., J. Phys. Chem., 69, 4166 (1965); Gunther H., Castellano S., Ber. Bunsenges. Phys. Chem., 70, 913 (1966)].
IV. 5. ,
0 : 1 H (O11 ), 2 H
(2652 ) 1 H (7284 ).
, (/=11 ),
H0 Hd- , 11 , 35 46 , 41 52 .
, .
: 35 41 , 46 52.
() , , 6 .
,
2632 , 6 . ,
, : 6( ) (H^). . H0
,
. , . ,
:
6(H 0 ) > () > 6(H 6 ) > 6( ) () > 6(H 0 ) > 6(Hc) > 6(H 4 ). , ,

451

V. 2

2 ,. .

_,,. .

-- 52 -- 2:- N sm = EN sm
8
2

/
a'-N sin ax = EN sin ax
, E = 2 2 /8 2 .
,
. L, .
1
X = OnX-L , . . F(O) = 4'(L) = .

W () = N sin a O = ;

W ( L ) = N sin aL =

, aL = qn, q . , = qn/L, . . :
Eq = (h2/8mL2)

= 1,2,3,...,

Wq = N sin qnx/L,

16*

W = 2/

452

V. 3. . 166.
: = f z (A) +/7(B) + / (). :
V

Y ( A - V B - vc)

\ = Y ( A + B + c)

-v c )

z = Y (VA + v B - vc)

V. 9. VA = 31,55 ; VB = 16,95 ; = 10,5 ; /, = / 4 = 0,42; /2 =


= / = 1,58.
V. 10. VA = 95,00 ; V 8 = 105,00 ; /AB = 6,00 .
V. 11. 1: / = 0,993; 2: / = 0,595.
V. 12. 1) -: 43,29, 45,78, 47,75 50,29 . 2)
-: 45,21, 47,75, 54,03 56,32 . ab- 2,52 | / | . ,

1)

VA

= 45,76 ;

V 0 = 51,86 ;
V

~ A + VB + V

/ (/i): <P I Ix (A) + Ix (B) I aa> = [<pa | /, (A) | aa> + <pa | Ix (B) | aa)] =

Pa |1 pa) + (pa y
2

/ (: (PP I Tx (A) + Ix (B) I ap} = [(PP I Ix (A) | ) + (pp | Tx (B) | ap>]

j PP) + (PP Y a a )] 2 =T
/(/) /(ft).

V. 6.

sin 29 = //2C = 15/25 = 0,6


f, =7,5 + 12,5 = 20,0;
/ 2 = - 7,5 + 12,5 = 5,0;
/ = 7,5 - 12,5 = - 5,0;

1: V A = 10,55 ;

/ = 3,5 :

/ 4 = 0,4

V B = 16,75 ;

/ = 11,5

2: V A = 15,7 ;
VB

//22 E

#23

//24

//32

//33 E

//34

//42

//44

B - v c ) + j (/AB - 'AC - 'BC)

COOH

A
= #42 =

'

#43 =

/ = 13,7 :

/ =0.78

/ = 1,3

CON H 2

H2N-C-Hx

A + V B + VC) + J (- /AB - / A C + /BC)

#23= #32= Y

= 11,7 ;

/=0.92

- , 1. L- , - . /AB
(. . 2.1 . IV).
- - H 8
- ; , , :

= Y ( V A - V B + v c ) + j (- /AB + /AC - /BC)

#44 = Y (-

/AX = 10,17 ; :
/ = - 2,03

2 | / ) , 10,2 .
,

/, = 0,4
/ 2 = 1,6

V. 7

VB

= 47,61 ;

X F. ,
19
F. ,
/ 9 , f 1 0 / (
V x , ): 6,66(0,822), 4,08(1,000)
2,15(0,178). (V. 26) , 2. , - napa-tt, F-
( 10,17 2,03). /,
-, . .
[34] (. . ).
V. 13. , . , /2 fa .
, -, 0,25 .
:

/=1,6

f 4 = - 7,5 - 12,5 = - 20,0;

2) V A = 50,00 ;

ab- I: 0,0 9,78 10,02 (19,8)


- 2: 6,2 16,2 20,4 30,8

= -^- V(v 0 6) 2 + / 2 = -I /400 + 225 = 12,5

-J ( A

/AX = I-67
/ = 6,47

111

V. 4.

453

/ AB

V. 8. a) 1/V3;
6) 1 : 3 : 3 : 1 ; s)
vo6 -,

CONHa

COOH

COOH

V. 15. , N = 9,0 ,
: L = 7,0, = 11,0 (7,0); M = 7,0 (11,0) . - : / = 8,0, /' = 1,0,
JA = 9,0 (2,0) Jx = 2,0 (9,0) .

454

V. 16. , N = 9,7 ; , ab
: 1) 0,0, 7,7, 10,6, 18,7 ; 2) 1,7, 7,4, 11,4, 16,9 .
, L = 7,4 7,8 (. . L = 7,6 ), = 7,9
M = 5,6 . ab
L, , ,
. - : / <= 8,6;
/' = 1,1; JA = 6,8 / = 1,1 . /
/23. '': 7 = 8,65, /' = 1,04, JA 6,79
= 1,03 ; , - .
VI. 1. ) ''"'"2;, ) ABX 2 ; ) ''; ) 4 ; ) ABCD;
) ''.
VI. 2. 2- ABCD-, [Kowalewski V. J., Kowalewski D. G.,
J. Chem. Phys., 37, 2603 (1962)]. 3-
IKowalewski V. ]., Kowalewski D. G., J. Chem. Phys., 36, 266 (1962)],
4- ''- ''-.
VI. 3. , ''-, .
VI. 4. ) (); ) (); ) ; ) ; ) ;
) ; ) ; ) ; ) : ) .
V I . 5. a) AX; ) AX; a) AX 2 ; ) ''; ) AX 2 Y; ) A 2 X 6 .

,
,
, .
, , .
.

, , , , . , , ,
.
(72 76) , 77 .
,
, .
,

1.
2.
.
4.
5.

6.

7.

8.
9.
BIO.

Abragam A., The Principles of Nuclear Magnetism, Clarendon Press, Oxford, 1961.
' "..
Andrews E. R., Nuclear Magnetic Resonance, Cambridge University Press,
Cambridge, 1955. ( : . . M.: , 1957.)
. Becker E. D., High Resolution NMR, Academic Press, New York, 1959.
Bovey P. A., Nuclear Magnetic Resonance Spectroscopy, Academic Press
New York, 1969.
Carrington A., McLachlan A. D., Introduction to Magnetic Resonance,
Harper & Row; New York, 1967. ( : ., . . .
M.: , 1970.)
Etnsley J. N., Feeney J., Sutcliffe L. H., High Resolution Nuclear Magnetic
Resonance Spectroscopy, Pergamon Press, Oxford, 1965, 2 vols. (
: ., ., . . M.: , . 1, 1968, . 2, 1969.)
Jackman L. M., Sternhell S., Application of Nuclear Magnetic Resonance
Spectroscopy in Organic Chemistry, Pergamon Press, Oxford, 1969.
Losche A., Kerninduktion, VEB Deutscher Verlag der Wissenschaften, Berlin, 1957. ( : . . M.: ,
1963.)
Mavel G., Theories Moleculaires de Ia Resonance Magnetique Nucleaire,
Dunold, Paris, 1966.
Poole C. P., Farach H., The Theory of Magnetic Resonance, Wiley-Interscience, New York, 1972.

456

457

. Bloembergen N. Nuclear Magnetic Relaxation. W. A. Benjamin New York


1961.
34. Corio P. L., Structure of High-Resolution NMR Spectra, Academic Press.
New York, 1966.
35. Ebert L, Seifert G., Kernresonanz im Festkorper, Geest und Porting Leipzig, 1966.
36. Emsley 1. W., Lindon J. C., NMR Spectroscopy Using Liquid Crystal Solvents, Pergamon, Press, Oxford, 1975.
37. Farrar T. C., Becker E. D., Pulse and Fourier Transform NMR, Academic
Press, New York, 1972. ( : ., . - . M.: , 1973.)
38. Fluck E., Die kernmagnetische Resonanz und ihre Anwendung in der anorganischen Chemie, Springer Verlag, Berlin, 1963.
39. Jackman L. M., Cotton F. A. (Editors), Dynamic NMR Spectroscopy Academic Press, New York, 1975.
40. LaMar G. N., Horrocks W. D., Holm R. H. (Editors), NMR of Paramagnetic Molecules, Academic Press, New York, 1973.
41. Lepley A. R., Class G. L., Chemically Induced Magnetic Polarization
Wiley, New York, 1973.
42. Leyden D. E., Cox R. H., Analytical Applications of NMR, Wiley New
York, 1977.
>
.
43. Memory J. D., Quantum Theory of Magnetic Resonance Parameters
McGraw-Hill, New York, 1968.
44. Mooney E. P.. An Introduction to 19F NMR Spectroscopy, Heyden-Sadtler
London, 1970.
45. Mullen K., Pregosin P. S., Fourier Transform NMR Techniques: A Practical Approach Academic Press, London, 1976.
46. Noggle J. H., Schirmer R. E., The Nuclear Overhauser Effect, Academic
Press, New York, 1971.
47. Poole C. P., Farach H., Relaxation in Magnetic Resonance Academic
Press, 1971.
48. Roberts J. D., An Introduction to the Analysis of Spin-Spin Splittings in
Nuclear Magnetic Resonance Spectra, Benjamin W. A., New York, 1961.
( : . . M.: , 1963.)
49. Shaw D., Fourier Transform NMR Spectroscopy, Elsevier, Amsterdam,

Bl 1. Pople J., Schneider W. G., Bernstein H. J., High-Resolution Nuclear Magnetic Resonance, McGraw-Hill, New York, 1959. ( :
., ., . . M.: , 1962.)
12. Silescu H., Kernmagnetische Resonanz, Springer Verlag, Berlin, 1966.
13. Slichter C. P., Principles of Magnetic Resonance, 2nd ed., Springer Verlag, Berlin, 1978. ( : . . M.: , 1981.)
14. Suhr H., Anwendungen der Kernmagnetischen Resonanz in der Organischen Chemie, Springer Verlag, Berlin, 1965.
15. Strelow H., Magnetische Kernresonanz und Chemische Structur, 2nd ed.,
D. Steinkopff, Darmstadt, 1968.

16. Bhacca N. S., Williams D. H., Application of NMR Spectroscopy in Organic Chemistry, Holden-Day, San Francisco, 1965. ( : H., . . M.: ,
1966.)
17. Bible R. H., Introduction to NMR Spectroscopy, Plenum Press, New York,
1965. ( : . . M.: , 1969.)
18. Clerk ., Pretsch ., Kernmagnetische Resonanzspectroscopie in der organischen Chemie, Akademische Verlagsgesellschaften, Frankfurt/Main, 1970.
19. Chapman D., Magnus P. D., Introduction to Practical High Resolution
NMR Spectroscopy, Academic Press, New York, 1966.
20. Dixon W. T., Theory and Interpretation of Magnetic Resonance Spectra,
Plenum Press, London, 1971.
21. Hecht H. G., Magnetic Resonance Spectroscopy, Wiley, New York, 1967.
22. Joseph-Nathan P., Diaz E., Introduction a Ia Resonancia Magnetica Nuclear, Limusa-Wiley, Mexico, 1970.
23. Lynden-Bell R. M., Harris R. K., Nuclear Magnetic Resonance Spectroscopy, Nelson, London, 1969.
24. Mathieson D. W. (Editor), Nuclear Magnetic Resonance for Organic Chemists, Academic Press, London, 1967.
25. McFarlane W., White R. F. M., Techniques of High-Resolution Nuclear
Magnetic Resonance Spectroscopy, Butterworths, London, 1972.
26. McLauchlan K. A., Magnetic Resonance, Clarendon Press, Oxford, 1972.
( : - . . . M.: ,
1976.)
27. Roberts J. D., Nuclear Magnetic Resonance, McGraw-Hill, New York, 1959.
( : . . M.: ,
1961.)
28 Schumacher R. ., Introduction to Magnetic Resonance W. A. Benjamin,
New York, 1970.
29. Zschunke A., Kernmagnetische Kernresonanzspectroscopie in der organ!schen Chemie, Akademie Verlag, Berlin, 1971. ( : .
. M.: , 1974.)

50. Sievers R. E., Nuclear Magnetic Resonance Shift Reagents Academic


Press, London, 1973.
51. Witanowski M., Webb G. A. (Editors), Nitrigen NMR, Plenum Press London, 1973.
52. Ziessow D., On-line Rechner in der Chemie, Grundlagen und Anwendungen in der Fourierspectroscopie, Walter de Gruytre, Berlin, 1973.
13C

53. Abraham R. J., Loftus P., Proton and Carbon-13 NMR Spectroscopv Hevden, London, !978.
54. Breitmeier E., Voelter W. 13 C-NMR Spectroscopie (Monographs in Modern
Chemistry, 5) Verlag Chemie, Weinheim/Bergstr, 1974
55. Breitmaier F Bauer G., 1 3 C-NMR-Spectroscopie, Georg Thieme Verlag
Stutgart, 1977.
56. Clerc J. T., Pretsch E., Sternhell S., l 3 C-Kernresonanzspektroskopie, Akademische Verlagsgesellschaft, Frankfurt/Main, 1973.
57. Levy G. C., Nelson G. L, Carbon-13 NMR for Organic Chemists, WileyInterscience, New York, 1972. ( : ., .
-13 ?
-. M.: , 1975.)

. Abraham R. ]., Analysis of High Resolution NMR Spectra, Elsevier, Amsterdam, 1971.
31. Axenrod T., Webb G. A. (Editors), Nuclear Magnetic Resonance Spectroscopy of Nuclei Other than Protone, Wiley, New York, 1974.
32. Bovey F. A., High Resolution NMR of Macromolecules, Academic Press,
New York, 1961. ( : .
M.: , 1967.)

458

58. Stothers J. ., Carbon-13 NMR Spectroscopy, Academic Press, New York,


1972.
59. Wehrli F. W., Wirthlin T., Interpretation of Carbon-13 NMR Spectra,
Heyden, London, 1976,

, , .


60. Casy A. F., NMR Spectroscopy in Medical and Biological Chemistry, Academic Press, London, 1971.
61. Dwek R. A., Nuclear Magnetic Resonance in Biochemistry: Application to
Enzyme Systems, Clarendon Press, Oxford, 1973.
62. Dwek R. A., Campbell I. D., Richards R. E., Williams R. J. P., NMR in
Biology, Academic Press, London, 1977.
63. Wuthrich K., NMR in Biological Research: Peptides and Proteins, Elsevier, Amsterdam, 1976,
64. Brugel W., Kernresonanz-Spektrum und Chemische Konstitution, D. Steinkopff, Darmstadt, 1967
65. Bovey F. -A., NMR Data Tables for Organic Compounds, Wiley, Interscience, New York, 1967.
66. Breitmaier E., Haas G., Voelter W., Atlas of Carbon-13 NMR Data, Heyden, London, 1975.
67. Data Bank 13C, Bruker-Physik, Karlsruhe, 1976.
68. Herschenson H. M., NMR and ESR Spectra Index, Academic Press, New
York, 1965.
69. Howell M. G., Kende A. S., Webb J. S., Formula Index to NMR Literature
Data, Plenum Press, New York, 1966, 2 vols.
70. Stadtler Standart NMR Spectra, Stadtler Research Lab., Philadelphia, 1967.
71. Varian High Resolution NMR Spectra Catalog, Varian Assoc., Palo Alto,
1963, 2 vols.

72. Waugh J. S. (Editor), Advances in Magnetic Resonance, Academic Press,
New York, 1968 ff.
73. Mooney E. F. (Editor), Annual Reports on NMR Spectroscopy, Academic
Press, New York, 1968 ff.
74. Emsley J. W., Feeney L, Sutcliffe L. (Editors), Progress in Nuclear Magnetic Resonance Spectroscopy, Pergamon Press, Oxford, 1966 ff.
75. Levy G. C. (Editor), Topics in Carbon-13 NMR Spectroscopy, Wiley, New
York, 1974 ff.
76. Diehl P., Fluck E., Kosfeld R. (Editors), NMR-Basic Principles and
Progress (NMR-Grundlagen und Fortschritte), Springer Verlag, Berlin,
1969 ff.
77. Harris R. K., Abraham R. J. (Editors), Nuclear Magnetic Resonance, Specialist Periodical Report, Chemical Society, London, 1972 ff.

*
, , , ,
. ,
* H. M. . . H. . .

459

IL

1. . . . M.: , 1975.
2. . ., P. 3., - M.
. : (), 1978.
3. . ^ . .
.: , 1967.
4. ' Jl. ., H. . -, - - . M.: , 1979.
5. . ., . . . . : (), 1980.
6. . ., . , . .
. --: , 1977.
7. H. M. . M.: , 1981.
8. . . M.: , 1978.
9. K-. M. .
M.: , 1980.
10. ( ). . . M. . .: , 1982.
. AuIt A., Dudek G. ., Protonen-Kernresonaz-Spektroskopie, UTR-Taschenbuch 842, D. Steinkopff-Verlag, Darmstadt, 1978.
12. Bates R. ., Beavers W. A., Carbon-13 NMR Spectral Problems, The Human Press, Crescent Manor, 1981.
13. Becker E. D., High Resolution NMR, Academic Press, New York, 1980.
14. Brevard C., Granger P., Handbook of High Resolution NMR Multinuclear,
John Wiley & Sons, New York, 1981.
15. Ernst L, 13 C-NMR-Spektroskopie, UTB-Taschenbuch 1061, D. SteinkopffVerlag, Darmstadt, 1980.
16. Fuchs P. L., Bunnell C. A., Carbon-13 NMR, Based Organic Spectral Problems, John Wiley, & Sons, New York, 1979.
17. Fukushima E., Roeder S. B. W., Experimental Pulse NMR: A Nuts and
Bolts Approach, Addison-Wiley, London, 1981.
18. Jardetzky 0., Roberts G. C. K., NMR in Molecular Biology, Academic Press,
New York, 1981.
19. Kaplan J. I., Fraenkel G., NMR of Chemically Exchanging Systems, Academic Press, New York, 1980.
20. Kasler F., Quantitative Analysis by NMR Spectroscopy, Academic Press,
New York, 1973.
21. Kleinpeter E., Borsdorf R., 13 C-NMR-Spectroskopie in der organichen Chemie, Akademie-Verlag, Berlin, 1981.
22. Levy G. C., Lichter R. L., Nelson G. L. Carbon-13 NMR for Organic Chemists, Wiley-Interscience, New York, 1982.
23. Levy G. C., Lichter R. L, Nitrogen-15 NMR-Spectroscopy, Wiley, New York,
1979.
24. Leyden D. E., Cox R. H. Analytical Application of NMR, Wiley, New York,
1977.
25. Martin M. L., Delpuech !.-}., Martin G. ]., Practical NMR Spectroscopy,
Heyden, London, 1980.
26. Michel D., Qrundlagen und Methoden der kernmagnetischen Resonanz,
Akademie-Verlag, Berlin, 1981.
27. NMP Imaging in Medicine, Eds. L. Kaufman, L. E. Crooks, A. R. Margiles,
Igaku-Shoin, New York, 1981.
28. NMR and Periodic Table, Eds. R. K. Harris, B. E. Mann, Academic Press,
New York, 1979.
29. Sandstrom /., Dynamic NMR Spectroscopy, Academic Press, New York,
London, 1982.

460


30. . . . : , 1978.
31. Ati.lt A'., fittlt M. R. Handy and Systematic C a t a l o g of NMR Spectra
1
13
( H, C), University Science "Books, Mill Valley, California, 1980.
32. Brelmeier E., Haus G., Voelter W. A t l a s of Carbon-13 NMR Data, Heyden,
London, 1973.
33. Bremser W., Ernst L., Franke B., Gehards R., Hardt A. Carbon-13 NMR
Spectral Data, Varlag Chemie, Weinheim, 1981.
34. Bremser W., Franke B., Wagner H. Chemical Shift Ranges in 13C NMR
Spectroscopy, Verlag Chemie, Weinheim, 1982.
35. Brugel W., Handbook of NMR Spectral Parameters., Heyden, London, 1979.
36. Carbon-13 NMR Spectral Data. A Living COM-microfiche Collection of
Reference Material, Verlag Chemie, 1981, 30000 Spectra of 23450 Compounds.
37. Chamberlain N. F., The Practice of NMR Spectroscopy, Plenum Press, New
York, London, 1974.
38. 13C NMR Data for Organometallic Compounds, Eds. B. E. Mann, B. F. Taylor, Academic Press, New York, 1981.
39. Johnson L. F., Jankowski W. C., Carbon-13 NMR Spectra, Wiley-Interscience, New York, 1972.
40. Pouchert C. J., Campbell J. R., The Aldrich Library of NMR Spectra,
vol. 1-11, Aldrich Chemical ., Milwaukee, 1974.
41. Pr etch E., Selbl J., Simon W., Clerk Th., Tabellen zur Strukturaufklarung
organischer Verbindungen mit spectroskopischen Methoden, Springer-Verlag, Berlin, Heidelberg, New York, 1981.
42. Sadtler Standard Spectra, Philadelphia, 1973, Vol. 134, Vol. 35: Chemical Classiffication, Vol. 3638: Chemical Shift Index.
43. Simons W. W., The Sadtler Handbook of Proton NMR Spectra, Sadtler
Philadelphia, 1978, 1254.
44. Wiberg . ., Nist B. J., The Interpretation of NMR Spectra, Benjamin.
New York, 1962.

45. . . , , 12, 15871610


(1978).
46. H. M., . . 13
C. . , 1978, . 47, . 477507.
47. Ales R. A., Stevens A. N., Griffiths J. R., NMR Studies of Metabolites in
Living Tissue. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley,
J. Feeney, L. H. Stucliffe, Pergamon Press, Oxford, Vol. 15, Part 1/2,
1982.
13
13
48. Anet F. A. L., Variable Temperature C NMR. In: Topics in C NMR
Spectroscopy, Ed. Q. Levy, Vol. 3, 1979.
49. Barfield M., Johnston M. D., Solvent Dependence of Nuclear Spin-Spin
Coupling Constants, Chem. Rev., 73, 5373 (1973).
50. Barfield M., Spear R. J., Sternhell S., A l l y l i c Interpreter! Spin-Spin Coupling, Chem. Rev., 76, 593624 (1976).
61. Batiz-Hernandez H., Bernheim R. A., The Isotope Shift. In: Progress in
NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliff, Pergamon
Press, Oxford, vol. 3, 1967, p. 6386.
52. Bodenhausen G., Multiple-Quantum NMR. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press,
Oxford, Vol. 14, part 4, 1980,
p. 137173.
1
53. Booth H., Application of H Nuclear Magnetic Resonance Spectroscopy to
the Conformational A n a l y s i s of Cyclic Compounds. In: Progress in NMR

461

Spectroscopy, Eds J. VV. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon


Press, Oxford, Vol. 5, p. 149481.
54. Bystrov V. F., Spin-Spin Coupling and Conformational States of Peptides.
In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney,
L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 11, Part 2, 1976, p. 4187.
55. Cockerill A. F., Davies G., Harden R. C., Rackham D. M. Lantanide Shift
Reagents for Nuclear Magnetic Resonance Spectroscopy, Chem. Rev., 73,
553588 (1973).
56. Crabb T. A., Nuclear Magnetic Resonance of Alkaloids. In: Annual Reports
on NMR Spectroscopy, Ed. G Webb, Academic Press, New York, Vol. 8,
1978, p. 2198.
57. Davies P. B., Conformations of Nucleosides and Nucleotides. In: Progress
in NMP Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 12, Part 3, 1978, p. 135225.
58. Davis I. C., Deb K. K., Analysis of Hydrogen Bond and Related Equilibria
by means NMR. In: Advances in Magnetic Resonance, Ed. J. S. Waugh,
Academic Press, New York, Vol. 4, 1970, p. 201270.
59. Diehl P., Harris R. K., Jones R. G., Sub-Spectral Analysis. In: Progress in
NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 3, 1967, p. 162.
60. Ditchfield R., Ellis P. E., Theory of 13C Chemical Shifts. In: Topics in 13C
NMR Spectroscopy, Ed. Levy G., Wiley Intersci., New York, Vol. 1, 1973,
p. 146.
61. EUeI E. L., Pietrusiewicz K.13 M., 13C NMR of Nonaromatic Heterocyclic
Compounds. In: Topics in C NMR Spectroscopy, Ed. G. Levy, Wiley
Interscience, New York, Vol. 3, 1979, p. 172283.
62. Ellett J. D. Multinuclear NMR Spectrometers. In: Advances in Magnetic
Resonance, Ed. J. S. Waugh, Academic Press, New York, Vol. 5, 1971,
p. 117176.
63. Elvidge J. A., Jones J. R., Chambers V. M. A., Evans E. A., Tritium NMR
Spectroscopy. In. Isotopes in Organic Chemistry, Eds. Bungel E., Lee G. C.,
Amsterdam/Elsevier, Vol. 4, 1978, p. 150.
64. Emsley J. W., Fluorine Copuling Constants. In: Progress NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press,
Oxford, Vol. 10, Part 3/4, 1976.
65. Ernst R. R., Sensitivity Enhancement in Magnetic Resonance. In: Advances
in Magnetic Resonance, Ed. J. S. Waugh, Academic Press, New York,
Vol. 2, 1966, p. 1136.
66. Ewing D. F., Two Bond Coupling between Protons and Carbon-13. In:
Annual Reports on NMR Spectroscopy, Ed. E. F. Mooney, Academic Press,
New York, Vol. 64, 1976, p. 389437.
67. Foster R., Fyfe G. A., Nuclear Magnetic Resonance of Organic ChargeTransfer Complexes. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley,
J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 4, 1969,
p. 190.
68. Flygare W. H., Magnetic Interaction in Molecules and an Analysis of
>
Molecular Electronic Charge Distribution from Magnetic Parameters. Chem.
Rev., 74, 653689 (1974).
69. Freeman R., Morris G. A., Two-Dimensional Fourier Transformation in
NMR. In: Bulletin of Magnetic Resonance, Ed. J. Howard Bradbury, The
Franklin Institute Press, Philadelphia, Vol. 1, 1979, p. 527.
70. Goldstein J. H., Watts V S., Rattet L. S. 13C, H. Sattelite NMR Spectra.
In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney,
L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 8, 1972, p. 103163.
71. Gordon R. E., Hanley P. E., Shaw D., Topical Magnetic Resonance. In:
Progress in NMR Spectroscopy, Eds. J W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 15, Part 1/2, 1982, p. 147.
72. Gray W. A. B , Computer Assisted Analysis of Carbon-13 NMR Spectral
Data. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney,

462

L. H., Sutcliffe, Pergamon Press, Oxford, Vol. 15, Part 3, 1982, p. 201
230.
73. Haigh C. W., Malllon R. ., Ring Current Theories in Nuclear Magnetic
Resonance. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. S u t c l i f f e , Pergamon Press, Oxford, Vol. 13, Part 4, 1979,
p. 303344.
74. Ham N., Mole T., The Application of NMR Organometallic Exchange
Reactions. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutliffe, Pergamon Press, Oxford, Vol. 4, 1969, p. 91 192.
75. Hansen P. E., Carbon-Hydrogen Spin-Spin Coupling Constants. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe,
Pergamon Press, Oxford, Vol. 14, part 4, 1981, p. 178295.
76. Hansen P, E., Long Range 13C-13C Coupling Constants. A. Review, Org.
Magn. Res., 11,215233 (1978).
77 Hinton J., Amis E. S., NMR Studies of Ions in Pure and Mixed Solvents,
Chem. Rev., 67, 367425 (1967).
78. Hoffman R. A., Line Shape in High-Resolution NMR, Advances in Magnetic Resonance Ed J. Waugh, Academic Press, New York, Vol. 4, 1970,
p. 87200.
79. Howarth O. W., Carbon-13 NMR of Peptides, and Proteins. In: Progress
in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 12, 1978, p. 140.
80. Inagaki F., Miyazawa T., Analysis of Molecular Conformations and Conformational Equilibria with the Lanthanide Probe Method, in: Progress in
NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 5, 1970, p. 132.
81. Kowalewski V. /., The INDOR Technique in High-Resolution Nuclear Magnetic Resonance, in: Progress in NMR Spectroscopy, Eds. J. W. Emsley,
J Feeney L. H. Sutliffe, Pergamon Press, Oxford, Vol. 14, Part 3, 1980,
p. 132.
82. Lambs R. E., Oldfield E., NMR of Membranes. In: Progress in NMR
Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon
Press, Oxford, Vol. 14, Part 3, 1980, p. 113136.
83. Laszlo P., Fast Kinetics Studied by NMR. In: Progress in NMR Spectroscopy Eds J. W Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press,
Oxford, Vol. 14, Part 4, 1979, p. 257270.
84. Lincoln S. F., Kinetic Applications of NMR Spectroscopy. In: Progress in
Reaction Kinetics, Eds. K. R. Jennings, R. B. Gundall, Pergamon Press,
Oxford, Vol. 9, 1977, p. 199.
85. Lindman B., Forsen S., Chlorine, Bromine and Iodine NMR. In: NMRBasic Principles and Progress. Grundlagen und Fortschritte, Eds. P. Diehl,
E. Fluck, R. Kosfeld, Springer Verlag, Berlin, Vol. 12, 1976.
86. Llndon J. C., Ferrige A. G., Digitization and Data Processing in Fourier
Transform NMR. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley,
J. Feeny, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 14, Part 1, 1980,
p. 2766.
87. Mansfield P., Morris P. G., NMR Imaging in Biomedicine. In: Advances
in Magnetic Resonance, Ed. J. S. Waugh, Academic Press, New York,
1982, 345 pp.
88. Mantsch H. H., Saito Hazime, Smith I. C. P., Deuterium Magnetic Resonance Applications in Chemistry, Physics and Biology, in: Progress in
NMR Spectroscopy, Eds. J. M. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 11, Part 4, 1977, p. 212266.
89. Marchand A. P., Stereochemical Application of NMR Studies in Rigid Bicyclic Systems, in: Methods in Stereochemical Analysis, Verlag Chemie,
Vol. 1, 1982, 244 pp.
90. Marshall .1. L., Carbon-Carbon and Carbon-Proton NMR Couplings: Applications to Organic Stereochemistry and Conformational Analysis. In: Methods in Stereochemical A n a l y s i s , Verlag Chemie, Vol. 2, 1983, 250 pp.

463

91. Martin C. /., Martin M.-L., The Stereochemistry of Double Bond, in: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe
Pergamon Press, Oxford, VoI 8, 1972, p. 165259.
15
92. Martin G., Martin M. L., Goueshard J.-P., -N-NMR Spectroscopy: In:
Basic Principles and Progress, Eds. P. Diehl, E. Fluck, R. Kosfeld, Springer Verlag, Berlin Heidelberg New York, Vol. 18, 1981, 382 pp.
93. Noth H., Wrackmeyer H., NMR Spectroscopy of Boron Compounds, in:
Basic Principles and Progress, Grundlagen und Fortschritte, Eds. P. Diehl
E. Fluck, R. Kosfeld, Springer Verlag, Berlin, Vol. 15, 1978, 370 pp.
94. O'Relly D., The Chemical Shift Calculations: In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. S u t c l i f f e , Pergamon Press
Oxford, Vol. 2, 1967, p. 163.
95. Orrell K. G., Nuclear Magnetic Resonance Spectroscopy of Paramagnetic
Species. In. A n n u a l Reports on NMP Spectroscopy, Ed. G. Webb, Academic
Press, New York, Vol. 9, 1979, p. 1 124.
96. Petrosyan V. S., NMP Spectra and Structures of Organotin Compounds.
In: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney
L. H. Sutcliffe, Pergamon Press,
Oxford, Vol. 11, Part 2, 1977, p. 115148'
97. Pregosin P. S., Kunz P. W., 31P and 13C NMR of Transition Metal Phosphine Complexes, in: Basic Principles and Progress, Eds. P. Diehl, E. Fluck,
R. Kosfeld, Springer-Verlag, Berlin Heidelberg New York, VoI 16
1979.
98. Rattle H. W. E., NMR of Amino-Acids, Peptides, Proteins: In: Annual
Reports on NMR Spectroscopy, Ed. G. A. Webb, Academic Press New
York, London, Vol. IA, 1981.
99. Redfield A. G., The Theory of Relaxation Processes, in: Advances in Magnetic Resonance, Ed. J. S. Waugh, Academic Press, New York VoI 1 1966
100. Richard C., Granger P., Chemically Induced Dynamic Nuclear and Electron
Polarisation CINDP and CIDEP, in: NMR Basic Principles and Progress. Grundlagen und Fortschritte, Eds. P. Diehl, E. Fluck R Kosfeld
Springer-Verlag, Berlin, Vol. 8, 1974, 127 pp.
101. Rowe J. J., Hinton I., Rone K. L, NMR Studies on the Biochemistry of
Biopolimers, Chem. Rev., 70, 157 (1970).
102. Rummens F. H. A., Van der Waals Forces and Shielding Effects inNMR-Basic Principles and Progress. Grundlagen und Fortschritte 'Eds
P. Diehl, E. Fluck, R. Kosfeld, Springer Verlag, Berlin, Vol. 10, 1975.
103. Sergeyev N. M., Nuclear Magnetic Spectroscopy of Cyclopentadienyl Compounds, in: Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney
L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 9, 1975, p. 71 144
104. Siddal T., Stewart W. E., Magnetic Non-Equivalence related to Symmetry
Considerations and Restricted Molecular Motion, in- Progress in NMR
Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. S u t c l i f f e , Pergamon
Press, Oxford, Vol. 5, 1970, p. 33147.
105. Smith P. /., Tupciauskas A. P., Chemical Shifts of 119 Sn Nuclei in Organotin Compounds, in: A n n u a l Reports on NMR Spectroscopy Ed Webb G
Academic Press, New York, Vol. 8, 1978, p. 291370.
106. Smith W. B., Carbon-13 NMR Spectroscopy of Steroids. In: Annual Reparts
on NMR Spectroscopy, Eds. Webb G., Academic Press, New York, Vol. 8,
107. Steigel A., Speiss H. W., Dynamic NMR Spectroscopy In- NMR Basic
Principles and Progress. Grundlagen und Fortschritte Eds P Diehl
E. Fluck, R. Kosfeld, Springer Verlag, Berlin VoI 15 1978
108. Slathers J. B., 13C NMR of Steroids, Org. Ma'gn. Res ' 10, 439464 (1977)
109. Szymanski S., Witanowski H., Gryff-Keller A., Problems in Theory and
Analysis of Dynamic Nuclear Magnetic Resonance Spectra In- A n n u a l
Reports on NMR Spectroscopy, Ed. Webb G., Academic Press New York
Vol. 8, 1978, p. 227289.
J l O . Void R. L., Void R. R., Nuclear Magnetic Relaxation in Coupled Spin
Systems. In: Progress in MMR Spectroscopy, Eds. J. W. Emsley, J. Feeney,

f
464

L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 12, Part 2, 1978, p. 79


133.
111. Wasylishen R. E., Spin-Spin Coupling between Carbon-13 and First Row
Nuclei. In: A n n u a l Reports on NMR Spectroscopy, Ed. E. F. Mooney, Academic Press, New York, Vol. 7, 1977, p. 246292.
112. Wehrli F. W., Nuclear Magnetic Resonance of the Less Common Quadrupolar Nuclei. In: A n n u a l Reports on NMR Spectroscopy, Ed. Webb G.,
Academic Press, New York, Vol. 9, 1979, p. 125219.
113. Werbelow L. G., Grant D. M., Intermolecular Dipolar Relaxation. In: Advances in Magnetic Resonance, Ed. J. C. Waugh. Academic Press, New
York, Vol. 9, 1977, p. 189299.
114. Williams E. A., Cargioli J. D., Silicon-29 NMR Spectroscopy. In: A n n u a l
Reports on NMR Spectroscopy, Ed. Webb G., Academic Press, New York,
Vol. 9, 1979, p. 221-318.
115. Wilson N. K., Slathers J. B., Stereochemical Aspects of 13C NMR Spectroscopy. In: Topics in Stereochemistry, Eds. E. L. Eliel, N. L. Allinger, Wiley
Interscience, New York, VoL 8, 1974, p. 1158.
116. Witanowski M., Slefaniak L., Webb G. A, Nitrogen NMR Spectroscopy.
In: Annual Reports on NMR Spectroscopy, Ed. E F. Mooney, Academic
Press, New York, Vol. 7, 1977, p. 118245.
117. Wrackmeier B., Carbon-13 NMP Spectroscopy of Boron Compounds. In:
Progress in NMR Spectroscopy, Eds. J. W. Emsley, J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 12, Part 4, 1979, p. 227259.
118. Wray V., Carbon-Carbon Coupling Constants: A Compilation of Data and
Practical Guide. In: Progress in NMR Spectroscopy, Eds. J. W. Emsley,
J. Feeney, L. H. Sutcliffe, Pergamon Press, Oxford, Vol. 13, Part, 3, 1979,
p. 177256.
119. Young R. N., NMR Spectroscopy of Carbanions and Carbocations. In: Progress in NMR Spectroscopy. Eds. J. F. Emsley, L. H. Sutcliffe, Pergamon
Press, Oxford, Vol. 12, Part 4, 1979, p. 261286.
120. lurcher R. F., The Cause and Calculation of Proton Chemical Shifts in
Non-conjugated Organic Compounds. In: Progress in NMR Spectroscopy,
Eds J W. Emsley, J. Feeney, L, H. Sutcliffe, Pergamon Press, Oxford,
Vol. 2, 1967, p. 205257.

-2 356
, N--, . 288
271, 421
1-- 271
-14,
297 . .
26, 237
96, 125, 418
, 60 214
220 Al 302
39
259
259

,
'3C 404
50
,
288
84 ., 287
84 .
- 133
,[3- 91
38, 39, 91, 417
39
270
271
53, 298
65
142
183

NMRIT/NMREN
203
LAOCOON 203


36
-

334
-3, 4,4--5- 68
, 4-- 196
86 .
101, 102
, --3,4,6-- 267

, - 84
-, 353
96
[10]- 96
2--1,6-- 220
2,5--1,6-- 168
2,7--1,6-- 220
2--1,6-- 220
1,6-- 96, 100, 422
1,6--, 310
[14]- 96, 98
1,6; 8,13---- 99, 100
101, 285
6]- 279 .
18]- 96, 278 .
278, 318
95, 418
83
, 13C 435, 436
- 1 H 1 1 H 419
19
- 376 .,
382, 383
'- 418
418
259
215
186
99
70, 71
168
219
38, 40, 89, 136
, 2-- 317
164
135, 417
32, 34, 36
85
171
40, 93, 413
4--1-- 196
- 290

466

209
1,3--, Tt 13C 389
1,2-- 71, 214
93 .
105
84, 112, 419
- 103, 419
- 196 .
,
363
- 419
1,2,3-- 58, 171
1,2,4-- 177
1,2,3-- 172
, 13-- 250
253, 283
, - 290
, 2-- 195
, 3,6-- 215
2,1,1 132
2,2,1 90
2,2,1] 291
1,1,1 ] 74
233, 427
256
429
310
33, 72
72
69
22
19
282
-1,3 90, 422
- , 55, 270
-
292
280
280
121
-- 103, 406
19F 377
274, 277
154
153
71
331
186
121 .

351
234
105

106

106
19, 146, 148
158
158
24
66
66, 304
26 .,
380
229
266
266
69
255

23
, -- 88
80
144, 145, 146
423
164, 165
19- 377
90
- 115 .
22

235
326
17
336
115, 130, 133
.
132
.
133
.
W- 132
304 .
356
316
304
304, .
1
H 2D) 327 .
1
H 19F) 326
14
N) 326
326

332
333
330
329
311 .

332 ,


122
150, 151
26, 51, 64
-()- 34
34
, 19F 373
1
H 34
13
C 431
72
166
167
272
273
41
, 216
219
270 .
, 344 .
3,3- 287
297
,

252, 263

() 318 .

320

() 344
265

-
336
1,3-, 4-- 127

23
-
-
137, 361
18
103
23, 137
233
, 356 .
295
339
,
CCB 419
V(H 1 H) 116
3
/(,) 126
, 111
113
112
- 406
343

467

80, 398
261
132
280
24
210
, - 13 323 .
221 .
54
90- 242
333
- 241, 245,
. -

248
246
- 241
364
242
\ 242

245

247
-

243

245
WAHUHA 365
245

241
-
235
- 244
247
241
243
- 249

242, 247
270 .
270 .
80
234
11, 12, 35
13C 390
35, 236
36, 157
321
367
F- 375
- 81
33, 72

468


145
19
180
228
30
153
35, .

240
14 N 297
240
256
240

85
287

85
13
- 328, 402
, 13 -
396, 432
122
245
, 328
340
237
26
HN 297 .
, 17
143
175
18
17
- 295
,(3- 91
39
257
142
/- 216
274
, '/( 13 C, 1 H) 410
93 .
96 .
93
95

101 .
13C 403
93
98
100
164
423
74, 334
202
352 .

- 133 .
122, 127
117
134
280
274
- 367

307
58, 161
-, T1 13C 389

63
24, 365
301
86 .
66
45
54
30
17
- 87
91
165
107,
420
81,
85, 286 .
, 80
- 56
- 40
254
37
416
80, 81
416
180
-
132 .
- 133
(...) 32
, 33, 73
208
17
197
49
49
347

44

358

336


75
231
22
22
95, 124, 327, 418, 422
- 212
1--- 353
1-- 215
96
1H 96
13
C 401
165
360
54
90
291
282
146
292
57, 163
252 ., 265
.
265 .
284 .
, 63
66
318
321
323
283
2-- 253
416, 421
- 177
417
145
Fz 165, 424
158, 423
216
105
331
47, 152
31, 98
352
99
49
49, 54
162
263
76
157
, -15,16--15,16- - 96, 98
418, 422
2,6-- 171

469
13

C 386
- 129
2---- 179
103
172
, 1 4 N 327
241
233, 240
, , 233
136
221
231
70
25
103
103
423
49, 54
167
- 177
, 13C
388
1 H 212
202
153, 154
202
40, 89
254, 294
274
355 .
233
20, 24
304 ., .
70, 71
64, 433
- 215
64
64
48
49
263
258
312

19
13

C 431 .
9
' F 373
1
H 40, 416 .
10, 22, 240
235 .
242 .
235 .
235
238
235

470

- 235
- 238
13C 410
106, 317
255
301
258
121, 124
125
355
412
154
155
( )
432
/, 74
158
159
222
Az 153

156
361

157
'' 200, 201
202
-
(
) 311
'' 188

190
190
199
191, 192
192

192

-
(
) 312

190

194
AB 159
- 149
170

152, 311

163
168

162

- 348
-
(
) 312
A 2 B ( AB 2 ) 171
172, 177

173

176

175

172,
177
- 176
426
176
ABC 187
ABX 176

178

178
184

178
- 177
- 181
ABX, 179
ABX 3 180
AMX 49, 51, 224, 302

312 .
- 323 .
-
(
) 311 .
AX 46, 150
- 304 .
45, . -
319, 321
321
216
68
109
31
144, 147
167
10, 17, 144
164
75
- 143, 208
23, 234, 241
69
13C 412
434
435
404,
431
- 401
399
401, 435
435
-- 404
- 13
1
C- H 410
,
388, 390



392
- 410
437
- 396, 431

397
388
411
394, 402
s- 407
'/( 1 3 C 1 H) 410
/?f 412
405,
406
405
399
- 400
402
396, 432
- 407
13
C113C 408
13
C11H 408
13
C1X 390
395
403
391
390
404
411
1H
19
F 400
405
12
- 390
13
- 390
- 395
. 410
390
400
. 392
392
397
386
388
388
394
391
433
400
.
\ 389, 410
.

471

390, 410 .
,
392
13C 222
411, 412
394
394
390, . -
-

389, 410

390, 410
-

407 .
396
406

406
388
397
398
397
s- 408
396, 431 .
434
434
387
329,
390

387


404
404
396
433

() 390 . ,
T1 389, 396
19
F . -19-
48, 162
58
56, 163
18
45, 142
170
187
142
165
148
315
17
- 304 .

472

- 13C113C 408
is C ) i9 F 410
13
C11H 409
19
F119F 381 .
1
H119F 381 .
1
H11H 41 ., 114 .
133 .
422

129

121 .

420

418
419
121, 127, 418

418
115
135

123
130
_ 137

45

68

47
- 119
__
58,
183, 313
45


59, 114 .
59
59, 123

137
-
133 .
121 .

115 .
135
123
130
137, 359, 365
47

58, 183,
313 .
365, 395
59, 123


137, 383
1
H 1 2 D 226
1
19
H 1 F 381 .
1
H 1 1 H, . -
13
13
C1 C 408
13
C119F 410
13
C11H 409
19F119F 381 .
234

234
235
-
(
) 311
- 244
66, 77
66
66
13C 396
19
F 374
363
13C 406
177

-

1
H-1H 59, 114 .
13C 396
.
19
F 373 .
1
H 81 .
176
48
- 34 .
- 34 .
19F 377
364
76
(TMC) 34
, 303
421
418, 422
2--5-- 168
2-- 177
40, 41
323

, 1
1
H- H 122
86, 93
259
170
221
273
295 .
159
- 82
242 .
2 - 238
-13 . 13C
17
,
30, 33
167

212
118
280
-19- 373 .
377,
384
380
-- 377
380
I 377
, 2,2-- 380
- 374
,
380
380
385
- 381 .
377, 400
- 383
374
378
- 381
.
374
377
373
376
374
, 1,2--1,1,2,2-380
372
45

91
55, 199, 418, 422
-

() 245, 333
-
() 334 .
335
248
337
335
- 339
337
336, 337
342
335
336
339
342

340
335
336
- 249

473

246, 339
249
336
335
336
- 340
343
341
-
() 337
334
249
-

343
340
335

341
s- 13 C-'- 408
(
)
341 .
54
252, 429
29, 79 ., 415 .
-13 396 .
-19 373
215
40, 105, 222
[3,2,2] 99
[3,3,3] 99
125, 409, 434
210
417, 421
-1,3 421
-1,4 134
421
-2,4--1 91
40, 88, 405, 407, 421

- 276
13 274
-, C 405

- 275
du 275
-1,3,5 90, 282, 420
282
7,7-- 282
277

420
13
- - 387

107, 420
1--7-- 282

474

99, 284
, Fe(CO) 3 289
417, 421
- 82
118
-2- 91
4----- 180
40, 419
- 102
209
101
- >,' 116, 123, 418
13
C 1 H 409
101
209
417
25
175

359 .
187
335
216
22, 26, 73
137
20
330

259
54
54
30, 79
30
342
97, 145
83, 399, 400

13 - 406
19
- 376
'- 80
215
219
261

19
47

47, 148
2 - 156

- 152, 311
2 - 173
- 178
''- 190
19
24
19
258 .
258 .
, 354
267
1,2--1,1,2,2--, 18F 380
81
197
- 418
341
, 1--1-- 168
1,1-- 55
1,2-- 224
- 418
92
-1,2-- 224
272, 416, 421 .

273, 416, 421


416, 421
11
230
320
345
229
147
26, 27
27
18
17 .

() 320
.
13 - 390 .
-- g- 18
, .


. . .

5
8
8
9


I.
.

15

1. . . . .
2.
3. . . .
4.

17
17
20
22
25
28

II.
29
1.
1.1.
1.2.
1.3. .
2. -
2.1.
2.2.

2.3. . . .
2.4. - .

29
32
35

37
41
41
48
53
58
62

III.
63
1.
2.
3.
4.
5.


63
. . . . 66
. . .
69

73

75

77

IV. -

79

1. , . . . . 7 9
1.1.
80

476

1.2.


80
1.3.

86
1.4. -
93
1.5. . . . . 1 0 1
1.6.

1.7. . . . 105
1.8.
107
1.9.
109
1.10. . . .
. . . .1 1 0
1.11.
4
2. -
114
2.1. - . . 115
2.2. - . . 121
2.3. - . . . . 130
2.4. - . . . . 1 3 7
2.5. -
139

141
V.
142
1.
2.
2.1.
3.

4.
4.1.
4.2. , -
(J11 = ).
4.3.
, -
(/i/-=* O)
4.4. AB
4.5. AX
4.6.

5. Vi /,-/ . . .
5.1. AB
5.2.
5.3.
5.4. -

142
143
144
146
148
148
149
153
159
162
163
168
168
170
187
202
207

VI.

200
1.
2.
3.
H D-

13

200
215
223
226

VII.
. II

477

1.
2.
3.
3.1.
3.2.
4.
4.1. Tt . . .
4.2.
4.3. -

VIII.

228
! . .
231
. ' . . . . 235
238
238
241
242
244
245
251

1.
1.1.
1.2.
1.3.
1.4.
1.5.
2.
'. . .
2.1.
2.2.
2.3.
2.4.
2.5.

3.
4. 14N

IX.

228

252
252
256
258
260
263
263
265
266
270
274
280
286
294
297
299

300

1.
300
2.
304
2.1. -
304
2.2. -
311
2.3.

316
2.4.
318
2.5. -
323
2.6.
326
2.7.
' . ' . ' . ' . . 329
2.8.
'.'.'. 330
3. -
' . . ' . ' . ' . 333
3.1. -.
334
3.2. , - . . '.
340
3.3.
342
4. .'
344
4.1. ( ) . . .' 345
4.2. ( ) . . .
347
4.3.
350

478

5.

5.1.
5.2. .

(-)
6.
7.
8. -

X. -19 -13 .
19

355
359
364
367
370

. . 372

1. F
1.1.
1.2. - ' 9 F 1 19 F 1H119F
2. 13C
2.1. 13C . . .
2.2.
2.3. - -13
2.4. - 13C

XI.

352
352

373
381
385
390
396
407
410
412

.415

I.
415
2. - HH
415
3. (V. 3) . . . . 423
4.
423
5.
424
6. AB 2
424
7. ''
427
8.
427
9. ,

429
10. 13C
432
II. ()
432
12. , , ()
438

446

448
455
458
465

!
, ,
: 129820, , -110, , 1- ., . 2, .




.
. . H.
H.
. ,:
.
.
3633
27.10.83. 03.05.84. 60X90'/ie.
1. .

. 15 . . . . . 30. . .-. 30. .-.


. 30,28. . 3/2562. 3800 . . 840. 4 . 90 .

129820, , -110, , 1- ., 2.
- 2
. ,
, 198052, . , -52, , 29.