Supplements to the 2nd Edition (Editor S. Coffey) of

RODD'S CHEMISTRY O F

CARBON COMPOUND S

A modern comprehensive treatis e

Edited by

M. F. ANSELLPh .D ., D .Sc . (London), F.R .I .C.

Department of Chemistry, Queen Mary College ,University of London (Great Britain )

Supplement t oVOLUME II ALICYCLIC COMPOUND S

Part C :

Polycarbocyclic compounds, excluding steroid sParts D and E : Steroids

VOLUME IICDE

Alicyclic Compounds ; Polycarbocyclic Compounds ; Steroid s

Preface

vi iOfficial publications ; Scientific journals and periodicals

xvList of common abbreviations and symbols used

xv i

Chapter 9. Polycarbocyclic Compounds with Separate Ring-Systems ,and Spiro Compounds

by A . COX

1. Introduction

.

.

.

.

12. Compounds with rings joined directly or through a carbon chain

13. Spiro compounds ; spirans .

5a. Preparative methods .

5b. Properties

.

8

Chapter 10. Polycyclic Compounds. Fused or Condensed Cyclic System sby A . CO X

1. The bicyclo [ 1 .1 .0] butane group .

. '

92. The bicyclo [2 .1 .01 pentane group .

1 03. The bicyclo [ 3 .1 .0] hexane group .

1 24. The bicyclo [4 .1 .0] heptane group .

1 35. The bicyclo [5 .1 .01 octane group .

1 56. The bicyclo [6 .1 .01 nonane group .

1 57. The bicyclo [ 2 .2 .0] hexane group .

1 68. The bicyclo [ 3 .2 .01 heptane group .

1 89. The bicyclo[4 .2 .01 octane group .

1 910. The bicyclo [6 .2 .0] decane group .

2 011. The bicyclo [ 3 .3 .0] octane group .

2 112. The bicyclo[4.3 .01 nonane group .

2 113. The bicyclo [4.4 .01 decane group .

2 214. Highly condensed systems .

22

Chapter 11 . Polycarbocyclic Bridged Ring Compounds

by R . G . FOSTE R

1 .

Introduction .

2 3

a. General methods of synthesis

2 4

b. Bredt's rule

2 5

c. Bridged carbonium ions

2 6d. Molecular orbital theory

2 7

e. Nuclear magnetic resonance spectroscopy (n .m .r .)

2 7

f. Fluxional molecules

.

2 8

2 .

The bicyclo [ 1 .1 .1 l pentane group .

2 9

3 .

The bicyclo[2 .1 .11 hexane groups .

2 9

Preparation, 29 -

4 .

The bicycloheptanc group .

3 1

a. The bicyclo [ 3 .1 .1 ] heptane group

3 1

Preparation, 31 -

b. The bicyclo [2 .2 .11 heptane group

3 1

Mechanism and structure, 31 - Preparation, 32 -

5 . Polycyclic compounds derived from cyclopentadiene .

3 2

a . Oligomerisation products of cyclopentadiene

3 2

6 . The bi- and tri-cyclooctane group .

3 4

Mechanism and structure, 34 -

a. The bicyclo[2 .2 .21 octane group

3 5

Preparation, 35 -

b. The bicyclo [ 3 .2 .1 ] octane group

3 6

Mechanism and structure, 36 - Preparation, 37 -

c. The tricyclo[ 3 .3 .0 .0 2 ' 8 1 octane group

3 8Hydrocarbons, 39 -

7 .

The polycyclo [ 3 .3 .1 ] nonane group

3 9a. The bicyclo [ 3 .3 .1 ]nonane group

3 9Preparation, 39 -

b. The tricyclo [ 3 .3 .1 .0 2 ' 8 1 nonane group

4 1

Mechanism, structure and reactions, 41 - Preparation, 42 -

c. The tricyclo[ 3 .3 .1 .0 3 '1 nonane group

.

42

Hydrocarbons, 42 - Alcohols, 42 - Carbonyl compounds and car-

boxylic acids, 43 -

d. The tetracyclo[3 .3 .1 .0 2 ' 8 .04 ' 6 ] nonane, triasterane, group

4 3

Hydrocarbons, 43 - Carbonyl compounds, 43 -8 .

The bicyclo [ 3 .2 .2] nonane group .

44

Preparation, 44 -

9 . The bicyclo [4.2 .1 1 nonane group .

44Preparation, 44 -

10 . The bicyclo[4 .2 .21 decane group .

46

Mechanism and structure, 46 - Preparation, 4 6

11 . The tricyclodecane group

47

a .

The tricyclo[ 3 .3 .2 .0 2 ' 8 ] decane group

4 7

Hydrocarbons and halogenated derivatives, 47 - Carbonyl compound s

and carboxylic acids, 47 --

b. The tricyclol3 .3 .1 .1 3 '] decane, adamantane, group

4 7Mechanism and structure, 47 - Preparation, 48 - Homoadamantane ,51 - Diamantane, 51 -

c. The tricyclo[4.4 .0 .03 ' 8 1 decane, twistane, group .

5 112 . The bicyclo[3 .3 .3] undecane group

5 2

Chapter 12 . Bicyclic Monoterpenoids

by R . T . BROWN

1. Introduction

.

5 32. The thujane group .

5 33. The carane group

.

5 84. The pinane group _

6 55. The norbornane group

7 6a. Camphene and related compounds .

7 6b. Bornane (camphane) derivatives

8 1c. Fenchane derivatives .

9 1

Chapter 13 . The Sesquiterpenoid s

by R . RAMAG E

1. Introduction .

9 52 .

Acyclic types

9 6(i) Hydrocarbons, 96 - (ii) Oxygenated derivatives, 96 --

3. Monocyclic types

9 74 . Cyclopentylcyclohexanes .

9 9(i) Hydrocarbons, 99 - (ii) Oxygenated derivatives, 99 -

5 .

Bicyclo[4 .1 .0]heptanes

.

.

100(i) Hydrocarbons, 100 - (ii) Oxygenated derivatives, 101 -

G .

Bicyclo[4 .4 .0] decanes

.

.

.

10 1(i) Hydrocarbons, 101 - (ii) Oxygenated derivatives, 103 -

7 .

Bicyclo[4 .3 .0] nonanes

10 58 .

Bicyclo [ 5 .3 .0] decanes

.

10 6(i) Hydrocarbons, 106 - (ii) Oxygenated derivatives, 106 -

9 .

Spiro compounds

.

.

.

.

106(i) Hydrocarbons, 106 - (ii) Oxygenated derivatives, 107 -

10 .

Polycyclic systems .

.

.

10 8(i) Hydrocarbons, 108 - (ii) Oxygenated derivatives, 110 -

11 .

Macrocyclic sesquiterpenes .

11 1(i) Hydrocarbons, 111 - (ii) Oxygenated derivatives, 113 -

Chapter 14 . Diterpenoids, Sesterterpenoids and Triterpenoids

by J . D . CONNOLLY and K . H . OVERTO N

1. Introduction .

11 52. Diterpenoids .

11 5a .

Bicyclic diterpenoids .

11 5(i) Unrearranged labdanes, 115 - (ii) Rearranged labdanes, 116 -

b. Tricyclic diterpenoids .

.

-

.

1 1 8

(i) Rearranged pimaranes, 118 - (ii) The abietane group, 119 -c. Tetracyclic diterpenoids

12 1

(i) The kaurane group, 121 - (ii) The atisirane group, 122 -

d. The cembrane group .

12 3e. Eremolactone .

12 4

3. Sesterterpenoids

12 5

4. Triterpenoids

12 7

(a) The fusidanes, 127 - (b) Group A, 129 - (c) Group B, 132 -

5. Laboratory synthesis

13 4

a. Diterpenoids

13 4

b. Triterpenoids .

136

Chapter 15, Steroids : Sterols and Bile Acids

by A . B . TURNE R

1 .

Introduction

_

14 32 . Geometry of the steroid nucleus .

14 3

3 .

Structure in relation to physical properties

144

4 .

Principal chemical reactions

146

(i) Colour reactions, 146 - (ii) The 3,5-cyclosteroid rearrangement an d

related reactions, 146 - (iii) Backbone rearrangements and related

reactions, 148 - (iv) Side-chain oxidation, 150 - (v) Epoxidation o fO 5 -stenols and related compounds, 152 - (vi) Reactions of 7-dchydro-

sterols, 153 - (vii) Stanols, 153 - (viii) Stanones, 153 - (ix) Remot eoxidation, 154 -

5 .

Individual sterols and related compounds

15 6a.

The cholesterol series .

15 6(i) Cholesterol and its derivatives, 156 - (ii) Methyl derivatives, 157 -

(iii) Epicholesterol, 157 - (iv) Cholestadienols, 158 - (v) Hydroxy-

cholesterols, 158 - (vi) Oxocholesterols, 160 -- (vii) Cholestanols, 16 0

- (viii) Phosphorous- and sulphur-containing steroids, 160 - (ix) Chol-

estanediols, 161 - (x) Oxidocholestanes, 161 - (xi) Cholestenes, 16 1

- (xii) Cholestenones, 162 - (xiii) Cholestenediones, 163 -

b. Ergosterol and related compounds .

16 4

(i) Ergosterol, 164 - (ii) Irradiation products of ergosterol, 167 -

c. Other sterols

.

16 8

(i) Sterols of algae, 168 - (ii) Phytosterols, 168 - (iii) Sterols fro m

marine invertebrates, 170 - (iv) Sterols from miscellaneous sources ,173 -

d. Miscellaneous structural type

17 36 .

Bile acids

17 6Additions

17 8

Chapter 16 . Steroids : Sex hormones; Adrenocortical hormone s

by P . G . MARSHAL L

1 . Sex hormones and related compounds

17 9

a . Oestrogens

179

b. The gestogens .

.

.

.

18 2

Stereoisomers of progesterone, 186 - Progestational activity an d

structure, 186 - Gestogenic 19-nor-steroids, 186 -

c. The androgens .

.

.

.

18 7Dehydroepiandrosterone, 187 - Testosterone, 188 - Physiologica lproperties of testosterone etc ., 188 -

d,

Homosteroids .

.

.

.

18 9e .

Synthesis of adrenocortical steroids .

19 0Dehydro derivatives of cortisone, etc ., 190 -

2 . Adrenocortical hormones .

19 0d. Aldosterone

19 03 . Cyclosteroids

19 14 . Dimeric steroid hormones .

19 15 . Halogenated steroids

19 1a. Oestrogens

19 1(i) Halogenation in ring A, 191 - (ii) Halogenation in ring D, 192 - -

b- Androgens

_

192(i) Halogenation in ring B, 192 - (ii) Halogenation in ring D, 192 -

c . Gestogens

-

192Halogenation in rings A and B, 192 -

6 . Other substituted steroids 19 3b .

Pregnane series -

-

19 3

Chapter 17. Steroids: Cardiotonic glycosides and aglycons ; Toad poisons, p . 19 5by P . G . MARSHAL L

Digoxin derivatives, 199 - Digitoxigenin and derivatives, 199 -Canatigenin (A 4-analogue of digitoxigenin), 200 - Uzarigenin an drelated compounds, 201 - Digitalis glycosides and aglycons, 202 -Digitoxigenone, 202 - Toad poisons, etc ., 20 2

Chapter 18 . Steroid Saponins and Sapogenins

by J . ELKS

1. The saponins .

20 52 . The sapogenins

_

20 7

Sources and isolation, 207 - Biogenesis, 210 - Physical properties ,2111 - New sapogenins, 211 - Aminospirostans, 223 - Reactions o fthe sapogenin side-chain, 225 -

Chapter 19 . Biogenesis of Terpenes and Sterol sby T . W . GOODWI N

1. Introduction .

.

.

23 72. Biosynthesis of mevalonate (MVA)

23 73. Hemiterpenes

23 8

4. Monoterpenes

24 15. Sesquiterpenes

24 76. Diterpenes

252

8 .

Triterpenes 25 9(i) General, 259 - (ii) Demethylation reactions, 265 - (iii) Alkylatio nat C(24), 268 -- (iv) Insertion of double bonds, 271 - (v) Spirostanols ,

273 - (vi) Cardenolides, 275 - (vii) Bufatenolides, 276 - (viii )

Ecdysones, 277 --

9 . The tetraterpenoids : the carotenoids

27 9

(i) Prephytoene, 279 - (ii) Desaturation of phytoene, 279 - (iii )

Cyclisation of lycopene, 282 - (iv) Xanthophyll formation, 284 - (v )

C4 5 and C 50 carotenoids, 285 - (vi) Biosynthesis in photosyntheti c

bacteria, 287 -

10. Terpenoid quinones .

_

28 9

Index

291