PROTON SPIN-SPIN COUPLING CONSTANTS

Appendix

C

P R O T O N SPIN-SPIN C O U P L I N G

CONSTANTS

In this tabulated material, proton-proton coupling constants are given for specific compounds and for typical structures. For specific compounds, a literature reference is given in the fourth column; this refers to the bibliography at the end of the table. For typical structures, the range of measured values is indicated. For both, the protons involved are specifically indicated in the third column, where necessary. The sign of the coupling is given as + or as — for specific compounds when this is known. If not actually measured but strongly indicated by analogy, the sign is given as ( + ) or ( - ) . If not determined and not strongly indicated by analogy, the sign is indicated as ± . For olefinic compounds (entries 102-136), geminal, vicinal, and allylic couplings are given together for convenience.

604

A. GEMINAL C O U P L I N G S

A. GEMINAL COUPLINGS (GEMINAL COUPLINGS FOR ETHYLENIC C O M P O U N D S ARE G I V E N I N S E C T I O N B)

No.

C o m p o u n d or structural type

(CPS)

J

gem

Ref.

a

1

CH

2

CH CC1

3

CH 1 CH Br

5

CH3CI

( - ) 9.2 (-)10.2 (-)10.8

4

6

CH F

(-)

9.6

4

7

CH C1

4

8 9

CH CN

( - ) 7.5 (-)16.9 (-)20.4

CH C0 H

(-)14.6

CH N0

(~)13.2

1-3 1

4

10 11

4

3

3

3

3

3

2

2

3

NC—CH —CN 2

3

2

3

2

13

CH3COCH3 CH3OH

14

CeHs · C H

15

N^

12

(-)12.4

1-3

( —)13.0

1-3 4 5

1-3 1-3

(~)14.9

3

y~cH

3

(-)10.8

1-3 4, 6

(-)14.4

1

(~)14.5

7

H(a)

16

j (CH —C—0) SO 3

H

2

( a )

—H

( b )

:

-10.45

8

1 H(b> H(a)

17

j (CH —C—0) CHCH 3

2

H ( a ) — H ( b > : —9.3

3

8

1 H(b) (-)7.63-9.95

18 H 19 H

20

/

H

C

=

N

^ O C H

(-)6.96-9.22

\

+ 40.22-42.42 (solvent dependent)

21

-3.9-8.8 Η

Η a

9, 10

(solvent dependent)

3

w

CH

9, 10

(solvent dependent)

OH

X

3

Η

K e y to references can be found o n page 6 2 6 .

605

11

A. No.

GEMINAL

COUPLINGS—(Continued) J

C o m p o u n d or structural type

gem

(cps)

Ref.

CI

H

H

24

+5.4-6.3

^^'1



H H

H

25

^ ^ ^ |

H

H

C H 3 ^ ° \ ^

H

H

H

26

C 27

N

*

+5.5

13

+5.4

14,16

+5.53

15

+5.78

15

+6.28

15

+5.65

15

+1.5

13

H

^

Η

Η

CH CO

Η

3

28

Η

Η

H0 C

Η

2

29

Η

Η

C H

Η

e

30

5

| « ^ ^

Η Η

Η ^ ^

Ν

Η

^ Η

31

Η C H ^

Η N

H ^ ^

Η

32

+2.0,

Η

33

|7|

^ ^ » |

Η

+3.4

16

Η

Η

606

<

0.4

17

A . GEMINAL C O U P L I N G S

A. No.

GEMINAL

COUPLINGS—(Continued) J

C o m p o u n d or structural type Br

H

H

gem

( a )

2

607

(cps)

Ref.

A.

No.

GEMINAL

COUPLINGS—(Continued)

J

C o m p o u n d or structural type

gem

608

(cps)

Ref.

A.

GEMINAL

COUPLINGS—(Continued)

B. VICINAL COUPLINGS Β. No. 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86

VICINAL COUPLINGS C o m p o u n d or structural type

CH3CH2— CH3CH3

( + )4.7 t o ca. ( + )9.0 + 8.0

C H C H 0 (Et) CH CH B(Et) CH CH OCH CH CH CH OAc (CH CH ) N CH CH C=CH CH CH C1 CH3CH CH CH CH COCH=CH CH CH Br CH CH N(Et) C H C H N (Et) CH CH I (CH CH ) C CH CH CN

( + )4.7 ( + )6.8 ( + )6.97 ( + )7.12 ( + )7.13 ( + )7.2 ( + )7.23 ( + )7.26 ( + )7.32 ( + )7.33 ( + )7.4 ( + )7.4 ( + )7.45 ( + )7.53 ( + )7.60 ( + )7.62 ( + )8.0 ( + )8.90 ( + )8.96 ( + )6.1 t o ( + )7.0 ( + )6.2

+

3

2

3

2

2

3

3

2

3

2

3

2

2

3

3

3

2

3

2

2

3

3

2

3

2

3

2

2

2

+

3

2

3

3

2

3

2

3

4

2

CH CH · CÔHS 3

2

(CH CH ) Si CH CH Li CH CH MgBr (CH ) CH— (CH ) CHOH (CH ) CHC1 (CH ) CHBr (CH ) CHI (CH ) CH-C H (CH ) CHCHO (CH ) CH CH CHC1 CH CHBr CH CHF 3

2

3

4

2

3

2

3

2

3

2

3

2

3

2

3

2

3

2

3

3

6

(+ (+ (+ (+ (+ (+ (+ (+ (+

5

2

3

3

2

3

2

3

Ref.

Jvie

2

— 31, 32 33 34 35 35 35 36 35 37 35 35 34 34 35 35 35 35 36 38 38 — 39, 39, 39, 39, 39, 39, 41 28, 28, 45

)6.4 )6.5 )6.6 )6.9 )7.0 )6.8 )6.10 )6.35 )4.5

Η J: ( + )8-12 Λ : ( + )2-4 t

87 Η CHOHC0 H

erythro:

( + )7.1

I

threo:

( + )4.3

2

89

90

CHDC0 H C1CH CH C1 2

2

(neat): ( + Jt'. ( + )18.0 ± J : ( + ) 9.2 ± [6.8] Ja v g (neat): ( + Jt' ( + )15.3 ± J \ ( + ) 3.4 ± [7.4]

BrCH CH Br 2

0.1

Javg

2

2

610

44

9

)6.8 ± 4.0 1.5

g

)8.30 ± 0 . 1 5 1.0 1.0

28

28

40 40 40 40 40 40 42 42

B. VICINAL C O U P L I N G S

V I C I N A L COUPLINGS—(Continued)

Β. No.

C o m p o u n d or structural type

91

Jvie

Ref.

C1 CHCH C1

A v s C n e a t ) : ( + )5.9 ± 0 . 1

28

Br CHCH Br C1 CHCHC1

/ : . ( + )10.5 ± 3.0 J : ( + ) 3.0 ± 1.5 [5.5] / (neat): ( + )6.65 ± 0.13 y g (neat) : ( + )3.06 ± 0.12 J : ( + )16.35 ± 0.80 J : ( + ) 2.01 ± 0.08 [8.1]

28 28

2

2

t

g

92 93

2

2

2

a v ?

2

a V

t

g

94

Br CHCHBr

95

CHC1 CHF

2

2

/ g (neat): ( + )2.92 ± 0.12 Λ ν * ( n e a t ) : ( + ) 3 . 0 9 ± 0.03 Jt' ( + )10.25 ± 0.40 J : ( + ) 2.01 ± 0.09 [4.8]

14, 28 45

H—H: +7.8-8.8

46

a v

2

2

9

Cl

96

meso: C H

dl:

97

dl:

CH

-CH

3

CH

meso: C H

CI

Η

Η

Cl

H

H

Cl

Br

Br

3

H

H

Br

H

3

H CH 98

99

(solvent d e p e n d e n t )

-CH

3

3

H — H : ( + )3.0-3.1

3

-CH

3

H — H : ( + )6.26-7.39 (solvent dependent)

46,47

-CH

3

H — H : ( + )3.28-3.45 (solvent dependent)

46,47

-C0 H

+10.7

48

-C0 H

+4.6, +10.9

49

Br 3

H

Br-

2

H

Br

H

H

Br-

2

H

46

(solvent d e p e n d e n t )

Br

611

V I C I N A L COUPLINGS—(Continued)

Β. No.

C o m p o u n d or structural type

Ρ

100

meso: C H

dl:

CH

H

( c )

CI CH

3

H(a)

H ) H a)

Ç1

H ) H a)

(b

-CH

H — H : ( + )2.0-2.9 H — H : ( + )10.6-11.4

50-52

H a)

53

(b)

(c)

(a)

3

(b)

( a )

( b )

(b

Φ CH

3

CH

50-52

(a)

(a)

H ) CI

meso: C H H a)

H(b) H a)

Φ

H b) H

(

H — H : ca. ( + )7.0 H — H : ca. ( + )7.0

(

3

Η(.ι

dl:

3

(

(b

H(a')

101

Ref.

H ) ~ H —H : ( + )7.45 H — C H : ( + )6.8 (

3

(b

(a)

(a)

(c)

3

(

(

( a )

-CH

3

H — H : ( + )9.75, ( + )5.05 ( + )12.5 ± 0.1 J : ( + )1.5 ± 0.1 (a)

3

(b)

53

J: t

g

H(a') H(b') φ (at 35°; highly temperature dependent)

C.

OLEFINIC COUPLINGS

No.

102

C o m p o u n d or structural type H(c)v

103

^c=c./

Ref.

H — H : - 3.2- +7.4 H — H : + 4.65-19.3 H — H : + 12.75-23.9 c i s : +11.5 ± 0.1*

H(s

:c=c:

(a)

(b)

(a)

(c)

Cb)

(c)

trans: gem:

+19.0

±



31,32,54

0.1*

+ 2.3 ± 0.2*

(asterisk = a v g o f 3 reports)

104

X=c:

105

:MgBr'

cis: trans:

Η

gem:

.Li

cis:

trans: gem:

106

107

LU

:c=c:

trans:

38

+22.1

+ 7.4 +19.3

55

+23.9

+ 7.1

c i s : +14.17; + 15.33

Si

:c=c:

+17.2

56, 57

+19.95; +20.47

g e m : + 4.38; +2.70 c i s : +11.76

trans:

Η

gem:

612

+18.37

+ 2.02

58

C. OLEFINIC

OLEFINIC

C. No. 108

110

COUPLINGS—(Continued)

C o m p o u n d or structural type FK FT

109

FU

:c=c;

.SCH

Jolef cis:

3

.C0 H

cis:

2

trans gem

.C0 C H

FU

111 FT

2

2

cis:

5

trans

H

gem:

χ

XOCFU

cis:

c:

trans gem:

X N

s

FU FT

114

FL FT

115

FU FU

116

117

FU

Hk FT

118

iU FU

119

trans gem

/CH

^c=c:

:c^c:

cis:

3

trans gem:

^CH F

trans gem:

/CHF

2

trans gem:

^c=c:" H

cis:

3

trans gem:

^CH C1

"c=c:

^CHC1

122

Hk

1.7

+ 11.7 + 0.24 + 10.77 +

1.10

+

+ 10.7 : + 17.5 : +

1.3

+ 10.02 +

2.08

+ 10.66 +

1.54

+ 10.85 +

0.67

+ 11.13

62, 63

: + 17.49

-

0.15

: + 16.80

+

0.22

: -

gem

: +

64

1.22

+ 9.69 trans : + 16.49 gem: + 1.25 cis:

65

0.42

+ 9.95 trans : + 16.78

613

62, 63

: + 17.49

cis:

2

62

: + 17.21

63

gem

XH I

61

: + 16.81

+10.07 trans : + 16.05

2

57

0.91

cis:

XH Br

56

: + 17.80

+ 10.14

gem: 3

60

: + 19.0

64

cis:

2

60

+ 10.11 trans : + 16.92 gem: + 1.27 trans

:c=c: x = c c

: +

cis:

2

^CC1

FU

cis:

"H

F T ^c=c:

121

cis:

2

^CF

FU

120

cis:

^-CeHs

^cc:

+ 10.2 : + 17.2

+ 11.75 trans : + 17.92

^c=c:

59

0.3

cis:

gem:

113

-

gem:

;c=cc

+ 10.3

Ref.

: + 16.4

trans

H"

112

COUPLINGS

64

OLEFINIC

C. No.

C o m p o u n d or structural type .OCH

123

F T :c=c: " H

124

H " :c=c:

+

3

gem: cis: gem: cis: gem: cis:

H " :c=cC^Br

Et0 C^ 2

cu

129

CK

130 CH

CH 0 C 3

132

3 ( 3 r >

gem:

:c=cC/ H 2

:c=cC" C 0 E t

3.2

+

7.4

-

1.3

+

7.1 1.8

67

trans : ( + )15.5

67

( + )5.2

67

: c = c c"H

trans : ( + )12.2

67

^W(2)

H( )

/ C = C ^

H ( a r " H b > : + 7.28 [H(b)— -H(b'): + 10.36]

68

+ 13.12 + 11.24]

68

H(i)-— H 2 ) : H(i)-— H : Η(2Γ —H : H(i)-—H : Η(2Γ —H :

+ 10.37

64

+ -

6.41 1.17

H(3)~ — H

-

1.43

+

9.97

( 3 )

3

/C-cC

H(a')

24

{ 2 )



H(D

cr

: ( + )2.0 : (-)l.O H(2)~ H ( ) : ( - ) 2 . 0

H(i)-~ H H(i)-~ H

"CÎ

:c=cc

.Cl

(

H(a) H ( a r H(b)'. [H(b>— -H(b')! —

-H(a)

:c=c:

(

(3)

\

H( )\^

( 3 )

^^.C(CH )

( 4 )

3

2

( 4 )

H(D

H(2)

H(i)- ~ H

135

Ho; H

136

(5

H \ H

66

/CI

H(a)>.

3

14, 66

( + )11.9

cis:

2

H(4)

134

66

/H

b

133

-

-

cis:

^C0 Et

:c=cC

2

Cl

4.65

trans : + 15.2

/H

131

2.0

+

trans : + 14.8

Hk

2

-

trans : + 12.75

:c=c: " H

Et0 C"

59

7.0

+ 14.1

.CI

126

128

Ref.

^H

FK

125

127

COUPLINGS—(Continued)

\

:c=c: ^ C ( N B u )

2

H(D

:

+ 17.01

Η(2Γ — H H(ir —H Η(2Γ — H Η(3Γ — H

+ 2.63 + 10.65

(

( 3 )

( 4 )

( 4 )

( 4 )

: : : :

2):

-

( 3 )

H(5

614

64

0.10 0.63

+ 10.17

+ 17.05 1.74 Η ( 2 Γ — H :: + H(i)- - H ( i ' ) :: + 1 0 . 4 1 H ( D - •—H ( 3 ) :

^ C - C ^ H(D

( 2 )

:

H(D-"H(3):

H(ir —H

^-FI(i')

( 4 )

+ 17.22 + 1.74

69

D. ADDITIONAL VICINAL ADDITIONAL

D. No. 137

138

VICINAL

COUPLINGS

COUPLINGS Ref.

C o m p o u n d or structural type HCeeCH

Η

Η

cis: trans

:

±9.8

31

±9.53

32

+

7.4-11.2

+

3.6-8.6

Η cis:

139

trans

+ 9.5 :

70

+ 5.5

Η ) :

+

8.0

:

+

4.6

H(b>—H(b')

+

10.5

H(c)

H(c')

+

11.0

H( )—H(c')

+

7.5

H )—H U

H a) (

140

H(b')

H a)

H(b)

( + )6.6

H(a)

H(c)

( + )3.6

H(c')

H(c')

H b)

Η( ' : 0

( A )

H(a>

142

H b) (

144

+

7.30

+ +

3.92 10.5

(

C

H(b-) H(c')

+

10.3

H( )

H(c')

+

6.6

cis :

+

9.2

trans :

+

5.4

H Η

cis : trans :

cis:

145

trans:

cis:

146

trans:

615

( + )7.5

H b)

Η

Η

( + )12.5

H( )

H

Η

}

H(c) B

Η

72

B

H(c)

H

71

H( '>: ( + ) 1 2 . 5

H(b>

(

143

( C )

B

(

141

( B

H

+11.2 +

71

12

12

8.0

+ 4 . 0 to + 5 . 0 + 1 . 9 to + 2 . 5

( + )4.45 ( + )3.10

13

D.

ADDITIONAL VICINAL

COUPLINGS—(Continued)

D. ADDITIONAL VICINAL

D.

ADDITIONAL

VICINAL

617

COUPLINGS

COUPLINGS—(Continued)

D.

ADDITIONAL VICINAL

618

COUPLINGS—(Continued)

D . A D D I T I O N A L VICINAL C O U P L I N G S ADDITIONAL VICINAL

D. No.

COUPLINGS—(Continued)

C o m p o u n d or structural type

Ref.

169

H )—H (avg'd v a l u e ) : ( + )3.8, ( + )7.1 (in C H C 1 )

77

H(2)—H : ( + )4.5 "H (in C H C 1 )

77

( 2

( 3 )

3

OH (equilibrates with equienergy mirror-image conformer when D = H) ( 1 )

( 3 e q )

170

( 3 a x )

OH H(ax)

3

D

(locked c o n f o r m a t i o n )

AcO

H 2ax)—H [H ax>—H H 2eq)—H (

171

( 4

(

[H

( 4

H

eq)

( 3 a X

) — ( + )10.0 = ( + )10.0] ) = (4-)5.0

78

( 3 a x )

( 3 a X

( 3 a

x)

=

( +

)5.0]

AcO

H

172

-H

(

1)

( :

H(i2eq)'

+ 2.5

78

+2.5

(171 and 172 are portions of 5-£-pregnan-3a, 12a-diol-20-one diacetate)

Js X X X X

173

619

e (cis) = F : ( + )1.2 = CI: ( + )2.4 = B r : ( + )2.8 = I: ( + )4.3

79

D.

No.

ADDITIONAL VICINAL

COUPLINGS—(Continued)

C o m p o u n d or structural t y p e

Ref.

Λe 174

(trans) = F:

X

79

( + )10.4

X

=

CI: ( + ) 1 1 . 4

X

=

Br: ( + )11.8

X

=

I:

( + )11.9

175

( + )8.1

80

( + )4.2

80

H(ax) H ( a x )

( + )9.42

28

H(ax) H ( q )

( + )2.72

176

Ho AcO

H(ax)

177

e

[H(eq)—H(eq)

H(4eq)

H(5

)

( + )7.02

H(4 q)

H(5eq)

( + )0.58

e

178

a x

H(5eq)—H(6ax)

( + )11.3

H(

( + )10.7

(

5 a x )

—H 6ax)' (

H 5eq)—H (

620

( 6

ax):

81

( + )3.06

H 5 a x ) — H 6ax) (

179

ca. ( + ) 2 . 7 ]

( + )2.6

81

621

D.

ADDITIONAL VICINAL

622

COUPLINGS—(Continued)

Ε.

AROMATIC RING

No.

COUPLINGS

C o m p o u n d or structural type

Ref.

+6.5-9.4

ortho: 193

194 Η

meta:

+0.8-3.0

para:

+0.4-1.0

ortho

:

7.5

meta

:

1.4

ortho

:

7.68

86

meta:

1.42

para:

0.60

Η

( Λ )

—Η(Β)ΐ

87

+7.1-8.1

( F o r R = Ν 0 : 8.4) 2

Η(Β) 195

Η(Β') : +1.1-1.7

( F o r R = Ν 0 : 8.0) 2

Η(Λ)

Η(Β') : +1.1-1.7

Η(Α)—Η(Α')

+0.3-0.6

:

( F o r R = Ν 0 : 0.1) 2

Η(Λ) Η(Β) : +1.8-1.9 (for R - Ν 0 : + 2 . 2 ) Η H : + 0 . 3 0.6 Η ( Β Γ Η ( ο : +7.8-8.1 (For R = N O , : + 8 . 3 ) 2

196

( Λ )

( C )

(Α) Η (β)"· + 8.5-8.7 (ForR = C H , R ' = I: +7.9)

88

( F o r R or R = N 0 :

88

Η

3

,

2

197

Η(ΛΓ—Η

( Λ

·), H

( D

)

Η

+8.9-9.0) ( Β

)

mostly:

+ 2.3-2.7 (extreme range: + 2 . 1 3.0) H(A')—H

( B )

:

+0.3-0.5

( + ) 1 . 7 - ( + )2.2

198

Ό*' OH

199

(+)2.3

89

( + )2.5

89

Br

OH 200

Clr^^iCI

CI

623

Ε.

No.

AROMATIC RING

COUPLINGS—(Continued) Ref.

C o m p o u n d or structural type OH

201

0

2

N r ^ > i N 0

N0

2

Η(Λ)H(B)

(Η)

( + )8.1

90

)

( + )6.4

H(B')

( + )!.!

Η -H

( B

Η(Λ)

Η( ')

Η(Λ)—

Λ

Η( ) —

Η(Β)

( + )8.3

Η( )

( + )6.5

Η(Λ)

Η(Β')

( + )1·2

Η(Λ)

Η(Α')

Λ

Η )

203

ίΒ

Β

Η(Α)—Η

204

Η(Β)

HETEROCYCLIC R I N G No.

89

2

202

Κ

( + )2.8

( Β )

:

( + )7.6

Η Β'):

90

90



(

COUPLINGS

C o m p o u n d or structural type

Ref. H

H( ) H( — H ( H —H 3

( + )4.5-5.5

4 )

( + )7.5-8.2

H 3

H(5)

H

H( )

( + )0.3-1.6 ( + )0.0-0.4

( 2

3

205

( 2

(

206

( 2

( 5 )

6

( + )5.5

H(3)

—H

H(2)

—H( ) :

( + )1.6 ( + )0.4

( 3 )

3

( 4 )

2

H(3)

H

( 4 )

( 5 )

( 6 )

: : :

( + )7.5-7.9 ( + )7.0-8.0 ( + )4.5_4.8

( 6 )

: ( + )0.3-1.2 : ( + )1.7-2.0 : ( + )0.75-0.9

2

( 4 )

:

2

( 5 )

2

( 6 )

H(3) H(4) H(3)

—H —H H

H( >-— H H( >-— H H( >-— H H(4) — H H(4)- — H H( - H 5)

624

:

6

—H H„, — H

208

( 5 )

( 5 )

( 6 )

( 5 )

( 6 )

( 6 )

: : : : :

91

( + )7.5 ( + )0.9

5 )

H(4)

207

( + )0.7-1.0

H : H( ) H( ) — H : H( ) — H ( : 2



ca. 0.0 ( + )0.7-0.9 ( + )0.0-0.3 ( + )7.8-8.2 ( + )1.5-1.8 ( )4.7-4.9 +





HETEROCYCLIC R I N G

F. No.

COUPLINGS—(Continued) Ref.

C o m p o u n d or structural type

H( ) H 4)

( + )1.4-2.0 ( + )3.1-3.8

H( )

( + )0.7-1.0

H

( 2

( a

H( ) H(4) H( )

( + )l-4 ( + )1.2 —

92

H

) ) )

H

) H ,) H c ) ( 3

H(4)

( + )3.2-3.8



H(5)

( + )1.7-1.9 ( + )0.4-0.9

( 3

( 2

210

211

(

(

H 212

CK

4

3

5

1 2

4

3

4

H( ) 5

2

( a

(

H(4

5

( 3

5

H 213

3

(

)—H 4) ) H( ) H ) H( )

^C0 H

( :

I)

(

H H

( i

I)

H(4)

( i

2)'

H( ) 5

H ) H( ) H ) H 4) H )—H ) H ) H( ) ( 2

214

3

(C

(

( 2

(4

( 2

5

H ) ) Η )

H( )

Η I) H( 2) H 1)

H( ) : H( :

( 3

215

(a

α

216

(

H H

3ÎT

217

(

1)

(

1)

H 2) H< 3) H 2) H 2) (

(

(

H<5) 5

5

5 )

93

)4.7-5.5 )3.3-4.0 )1.3-1.5 )2.7-3.2



+ + + +

94

]H

:

Η

+1.2-1.5 +2.7-3.2 4.9-5.4

3 )

3

4

( 4 )

5 )

(

( i

3

(

4

( i

(5

625



H ( 2 ) : ca. ( + )3 H ( : ca. ( + )2 H( ) : ( + ) 2 . 4 - 3 . 1 H( ) : ( + ) 3 . 4 - 3 . 8 H : ( + )1.3-1.5 H ( :ca. ( + )2

(

H ^ H

4.7 3.35 1.0 2.85

+ 3.4-4.0 + 4.5-5.2 + 1.1-1.7

H(4)

H(4)

+ 3.5 + 1.8 + 0.8

(+ H ) H 2) (+ H ) H(3) • H 2) H( ) (+ (+ H :Ϊ ) H( ) H 2) H ( 4 ) (+ 2)~~H ) . c a . ( + (

3

4

218

(+ (+ (+ (+

"H{3)

H c 3)~~H( 4 )

S



H ) H ) H ) ( 2

209

)2.43 )2.43 )2.63 )3.42 )1.44 )2

95

K e y t o references : 1. M. Barfield a n d D . M . Grant, / . Am. Chem. Soc. 8 3 , 4 7 2 6 (1961).

2. M. Barfield and D . M. Grant, / . Chem. Phys. 36, 2054 (1962).

3. M . Barfield and D . M. Grant, / . Am. Chem. Soc. 8 5 , 1901 (1963).

4. H. J. Bernstein and N . Sheppard, J. Chem. Phys. 37, 3012 (1962).

5. P. J. Black a n d M. L. Heffernan, Australian J. Chem. 15, 862 (1962). 6. J. F. Bagli, P. E. Marand, a n d R. Gaudry, J. Org. Chem. 2 8 , 1207 (1963). 7. D . P. B i d d i s c o m b e , E. F. G. H e r i n g t o n , J. J. L a w r e n s o n , a n d J. F. Martin, J. Chem. Soc. 1963, 444. 8. F. K a p l a n a n d J. D . R o b e r t s , / . Am. Chem. Soc. 8 4 , 1053 (1962). 9. B. L. Shapiro, S. J. Ebersole, a n d R. M . K o p c h i k , J. Mol. Spectry. 1 1 , 201 (1963). 10. B. L. Shapiro, S. J. Ebersole, G. J. Karabatsos, F. M . Vane, a n d S. L. M a n a t t , / . Am.

Chem. Soc. 85, 4041 (1963). 11. B. L. Shapiro, R. M. Kopchik, and S. J. Ebersole, J. Chem. Phys. 39, 3154 (1963).

12. D . J. Patel, Μ. Ε . H . H o w d e n , a n d J. D . R o b e r t s , / . Am. Chem. Soc. 8 5 , 3218 (1963).

13. 14. 15. 16. 17. 18. 19.

F. S. Mortimer, / . Mot. Spectry. 5, 199 (1960). F. A. Bovey, Chem. Eng. News. 4 3 , 98 (1965). C. A. Reilly and J. Swalen, / . Chem. Phys. 3 2 , 1378 (1960). H. S. G u t o w s k y , M. Karplus, and D . M. Grant, / . Chem. Phys. 3 1 , 1278 (1959). J. I. Musher and R. G. G o r d o n , J. Chem. Phys. 36, 3097 (1962). K. L. Servis and J. D . Roberts, / . Phys. Chem. 67, 2885 (1963). K. Takahashi, T. Stone, Y. Matsuki, and G. H a z a t o , Bull. Chem. Soc. Japan 36, 108

(1963). 20. E. Lustig, private c o m m u n i c a t i o n q u o t e d by A . A . Bothner-By. (see f o o t n o t e 4, Chapter V ) . 21. R. R. Fraser, R. U . Lemieux, a n d J. D . Stevens, J. Am. Chem. Soc. 8 3 , 3901 (1961). 22. R. J. A b r a h a m and K. A . M c L a u c h l a n , Mol. Phys. 5, 195 (1962). 23. F. A . Bovey and F. P. H o o d , unpublished observations.

24. N . Muller and P. J. Schultz, J. Phys. Chem. 68, 2026 (1964). 25. F. A. L. A n e t , / . Am. Chem. Soc. 84, 1053 (1962).

26. K. B. Wiberg, B. R. Lowry, a n d B. J. Nist, / . Am. Chem. Soc. 8 4 , 1594 (1962).

27. D . H. Williams and N . S. Bhacca, Chem. Ind. (London) 1965, 506 (1965).

28. N . Sheppard and J. J. Turner, Proc. Roy. Soc. A 2 5 2 , 506 (1959). 29. J. S. W e b b , R. W . Broschard, D . B . Cosulick, J. H . M o w a t , a n d J. E. Lancaster, / .

Am. Chem. Soc. 84, 3183 (1962).

30. H. S. G u t o w s k y and C. Juan, J. Chem. Phys. 37, 120 ( 1 9 6 2 ) ; Discussions Faraday Soc. 34, 52 (1962). 31. D . M. G r a h a m and C. E. H o l l o w a y , Can. J. Chem. 4 1 , 2 1 1 4 (1963). 32. R. M . Lynden-Bell a n d N . Sheppard, Proc. Roy. Soc. A 2 6 9 , 385 (1962). 33. S. Brownstein, B. C. Smith, G. Ehrlich, and A . W . Laubengayer, J. Am. Chem. Soc. 81, 3826 (1959). 34. A . G. Massey, E. W. Randall, a n d D . Shaw, Spectrochim. Acta 20, 379 (1964). 35. S. E. Ebersole, S. Castellano, a n d A . A . Bothner-By, J. Phys. Chem. 6 8 , 3420 (1964) 36. P. T. N a r a s i m h a n and M . T. R o g e r s , / . Am. Chem. Soc. 8 2 , 5983 (1960).

37. D . R. Whitman, L. Onsager, M. Saunders, and H . E . D u b b , / . Chem. Phys. 3 2 , 67,

(1960). 38. G. Fraenkel, D . G. A d a m s , a n d J. Williams,

Tetrahedron Letters

39. A. A. Bothner-By and R. E. Glick, / . Chem. Phys. 25, 362 (1956). 40. J. Ranft,

Ann. Physik

[7] 10, 1 (1962).

41. J. S. Waugh and F. W. D o b b s , / . Chem. Phys. 3 1 , 1235 (1959).

626

1963, 767.

References

627

42. R. J. A b r a h a m and K. G. R. Pachler, Mol. Phys. 7, 165 (1964).

43. G. W . Flynn and J. D . Baldeschwieler, J. Chem. Phys. 37, 2907 (1962). 44. F. A . L. Anet, J. Am. Chem. Soc. 82, 9 9 4 (1960). 45. H . S. G u t o w s k y , G. G. Belford, a n d P. E . M c M a h o n , / . Chem. Phys. 36, 3353 (1962). 46. A . A . B o t h n e r - B y and C. N a a r - C o l i n , / . Am. Chem. Soc. 84, 743 (1962).

47. F. A . L. Anet, / . Am. Chem. Soc. 84, 747 (1962).

48. R. F r e e m a n and K. G . R . Pachler, Mol. Phys. 5, 85 (1962). 49. R. F r e e m a n , K. A . M c L a u c h l a n , J. I. Musher, a n d K. G. R . Pachler, Mol. Phys. 5, 321 (1962). 50. D . D o s k o c i l o v a , J. Polymer Sci. B2, 421 (1964). 51. D . D o s k o c i l o v a a n d B. Schneider, Collection Czech. Chem. Commun. 29, 2290 (1964). 52. T. S h i m a n o u c h i , M . T a s u m i , a n d Y . A b e , Makromol. Chem. 86, 34 (1965). 53. F. A . B o v e y , F . P. H o o d , E . W . A n d e r s o n , a n d L. C . Snyder, / . Chem. Phys. 42, 3900 (1965). 54. G. S. R e d d y and J. H . G o l d s t e i n , / . Mol. Spectry. 8, 475 (1962). 55. C. S. J o h n s o n , M. A . Weiner, J. S. W a u g h , and D . Seyferth, / . Am. Chem. Soc. 83, 1306 (1961).

56. 57. 58. 59. 60.

S. Castellano and J. S. W a u g h , J. Chem. Phys. 37, 1951 (1962). R. T. H o b g o o d , Jr., R. E. M a y o , and J. H . Goldstein, / . Chem. Phys. 39, 2501 (1963). W. A . A n d e r s o n , R. Freeman, and C. A . Reilly, / . Chem. Phys. 39, 1518 (1963). R. T. H o b g o o d , Jr., G. S. Reddy, and J. H . Goldstein, J. Phys. Chem. 67, 110 (1963). Y . Arata, H. Shimizu, and S. Fujiwara, / . Chem. Phys. 36, 1951 (1962).

71. B. J. N i s t , " A N u c l e a r Magnetic R e s o n a n c e S u m m a r y o f Small R i n g C o m p o u n d s " (unpublished) (1962). 72. H . M . H u t t o n a n d T. Schaefer, Can. J. Chem. 41, 2 7 7 4 (1963). 73. L. F. J o h n s o n , V. G e o r g i a n , L. G e o r g i a n , a n d Α . V. R o b e r t s o n , Tetrahedron 19, 1219 (1963).

74. E. Lustig, J. Chem. Phys. 37, 2725 (1962).

75. L. D . Hall, Chem. Ind. (London) 1963, 950.

76. 77. 78. 79.

F. A . L. A n e t , R. A . B. Bannard, a n d L. D . Hall, Can. J. Chem. 41, 2331 (1963). R . U . L e m i e u x a n d J. W . L o w n , Tetrahedron Letters 1963, 1229. N . S. Bhacca a n d D . H . Williams, / . Am. Chem. Soc. 86, 2742 (1964). A . N i c k o n , M. A . Castle, R. H a r a d a , C. E . Berkoff, a n d R. D . Williams, / . Am.

Chem. Soc. 85, 2185 (1963).

80. R. U . L e m i e u x a n d J. H o w a r d , Can. J. Chem. 41, 308 (1963).

81. Y . Fujiwara and S. Fujiwara, Bull. Chem. Soc. Japan 37, 1010 (1964). 82. J. M a s s i c o t and J. P. Marthe, Bull. Soc. Chim. France 1962, 1962. 83. F. A . L. Anet, Can. J. Chem. 39, 789 (1961). 84. P. Laszlo and P. v o n R. Schleyer, J. Am. Chem. Soc. 85, 2 0 1 7 (1963). 85. G. V. Smith a n d H . Kriloff, / . Am. Chem. Soc. 85, 2 0 1 6 (1963). 86. A . S a u p e , Z. Naturforsch. 20b, 572 (1965).

87. S. Castellano and C. Sun, / . Am. Chem. Soc. 88, 4741 (1966). 88. J. Martin and Β. P. Dailey, / . Chem. Phys. 37, 2594 (1962).

89. H . M . H u t t o n , W . F . R e y n o l d s , a n d T. Schaefer, Can. J. Chem. 40, 1758 (1962). 90. N . J o n a t h a n , S. G o r d o n , and Β. P. D a i l e y , / . Chem. Phys. 36, 2443 (1962).

91. V. G. K o w a l e w s k i a n d D . G. de K o w a l e w s k i , / . Chem. Phys. 36, 266 (1962). 92. G. S. R e d d y and J. H . G o l d s t e i n , J. Am. Chem. Soc. 84, 583 (1962). 93. R. F r e e m a n a n d D . H . Whiffen, Mol. Phys. 4, 321 (1961).

94. R. Freeman and N . S. Bhacca, / . Chem. Phys. 38, 293 (1963).

95. R. J. A b r a h a m a n d H . J. Bernstein, Can. J. Chem. 39, 905 (1961).

628

References

61. A. A . Bothner-By and C. N a a r - C o l i n , J. Am. Chem. Soc. 83, 231 (1961). 62. S. Castellano, private c o m m u n i c a t i o n q u o t e d by A . A . Bothner-By (see f o o t n o t e 4, Chapter V). 63. H. Gunther, private c o m m u n i c a t i o n quoted by A . A . Bothner-By (see f o o t n o t e 4, Chapter V). 64. A. A . Bothner-By, C. N a à r - C o l i n , and H . G u n t h e r , / . Am. Chem. Soc. 84, 2748 (1962); A. Bothner-By a n d H . Gunther, Discussions Faraday Soc. 34, 127 (1962).

65. S. Castellano and G. Caporiccio, / . Chem. Phys. 37, 1951 (1962). 66. C. N . Banwell and N . Sheppard, Discussions Faraday Soc. 34, 115 ( 1 9 6 2 ) ; C. N . B a n well, N . Sheppard, and J. J. Turner, Spectrochim. Acta 11, 7 9 4 (1960). 67. N . Muller, J. Chem. Phys. 37, 2729 (1962).

68. R. K. Harris, private c o m m u n i c a t i o n quoted by A . A . Bothner-By (see f o o t n o t e 4, Chapter V). 69. R. T. H o b g o o d , Jr. and J. H . G o l d s t e i n , J. Mol. Spectry. 12, 76 (1964). 70. S. M e i b o o m and L. C. Snyder, J. Am. Chem. Soc. 89 1038 (1967).