RODD'S CHEMISTRY

OF CARBON COMPOUND S

A modern comprehensive treatis e

SECOND EDITIO N

Edited by

S . COFFE Y

M.Sc . (London), D .Sc . (Leyden), F .R.I .C .formerly of

I.C.I . Dyestuffs Division, Blackley, Manchester

VOLUME II PART C

POLYCARBOCYCLIC COMPOUNDS ,

EXCLUDING STEROIDS

PREFACE VI IOFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS X VLIST OF COMMON ABBREVIATIONS AND SYMBOLS USED XV I

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

N. A. J . RoGERs

1 . General introduction to polycarbocyclic compounds ; classification and

nomenclaturea. Classification Ib. Nomenclature 2

(i) Ring-systems joined directly or through a carbon chain, 3 - (ii) Spir ocompounds, 3 - (iii) Fused and bridged ring-systems, 4

2 . Compounds with rings joined directly or through a carbon chain 5a. General methods of synthesis 6b. Polycyclopropyl compounds 6c. Polycyclobutyl compounds 9d. Polycyclopentyl compounds 9e. Cyclopropylcyclopentane compounds 1 3f. Cyclopropylcyclohexane compounds 1 3g. Cyclobutylcyclohexane compounds 1 3h. Cyclopentylcyclohexane compounds 1 4i. Polycyclohexyl compounds 1 4

(i) Hydrocarbons, r4 - (ii) Hydroxy and amino derivatives, 15 - (iii)Ketones, 16 - (iv) Carboxylic acids, Iq

j. Cyclopentylcycloheptane compounds 1 7k. Cyclohexylcycloheptane compounds 1 81 . Bicycloheptyl and its derivatives 1 8m . Bicyclo-octyl and related compounds 1 8

3 . Spiro compounds ; spiranes 2 0a. The spiro[z .z]pentane group 2 1b. The spiro[2 .3]hexane group 2 2c. The spiro[z .4]heptane group 2 3d. The spiro[2 .5]octane group 24e. The spiro[2,6]nonane group 2 5f. The spiro[3 .3]heptane group 2 5g. The spiro[3 .4]octane group 2 6h. The spiro[3 .5]nonane group 2 6i. The spir0[4 .4]nolla1le group 2 7j. The spiro[4 .5]decane group 2 9k. The spiro15 .5]undecane group 30

1 . The spiro[5 .6]dodecane group 3 1m.The spiro[6 .7]tetradecane group 31

Chapter io . Polycarbocyclic Compounds .

Fused or Condensed Cyclic Systems

N. A. J . ROGERS

i . The bicyclo[i .I .o]butane group 3 22 . The bicyclo[2 .1 .o]pentane group 3 53 . The bicyclo[3 .1 .o]hexane group 3 64 . The bicyclo[4 .I .o]heptane group 3 85 . The bicyclo[S.I .o]octane group 3 96. The bicyclo[6.I .o]nonane group 4 17 . The bicyclo[7 .r .o]decane group 4 28 . Bicyclo[2 .2 .o]hexane and related compounds 4 2

a. Bicyclo[z .2 .o]hexane and its derivatives 4 2b. Compounds related to tricyclo[4 .2 .o .o 2 . 6 ]octane 4 3c. Cubane and its derivatives 44d. Derivatives of prismane 4 5

9 . The bicyclo[3 .2 .o]heptane group 451o . The bicyclo[4 .2 .o]octane group 4711 . The bicyclo[5 .2 .o] nonane group 5o12 . The bicyclo[6.2 .o]decane group 5 013 . The bicyclo[3 .3 .o]octane (pentalane) group 3 114 . The bicyclo[4 .3 .o]nonane (hydrindane) group 5 515 . The bicyclo15 .3 .o]decane group 5916 . The bicyclo[4 .4 .o]decane (decalin) group 6 o

a. Saturated compounds 6 2b. Unsaturated compounds 6 8

17 . The bicyclo[5 .4 .o]undecane group 7 218 . The bicycio[5 .5 .o]dodccane group 7 219 . The bicyclo[6 .6.o]tetradecane group 7 32o . Highly condensed alicyclic systems 73

Chapter I I . Polycarbocyclic Bridged Ring Compounds

J . D . LITTLEHAILE S

1 . Introduction 7 7a. Synthesis and general properties of bridged ring compounds 7 8b. Bridged carbonium ions 8 o

2 . The bicyclo [I .I .I] pentane group 8 43 . The bicyclo[2 .I .I]hexane group 8 44 . The bicycloheptane group 8 8

a. The bicyclo[3 .I .I]heptane group 8 8b. The bicyclo[2 .2 .I]heptane (norbornane) group 8 9

(i) Saturated hydrocarbons, 89 - (ii) Unsaturated hydrocarbons, 89 - (iii )Alcohols, 91 - (iv) Carbonyl compounds, 95 - (v) Carboxylic acids, 9 6

5 . Polycyclic compounds derived from cyclopentadiene 99a. Polymerisation products of cyclopentadiene 99

b. Perhydrodimethanonaphthalenes (dimethylenedecalins) and thei rderivatives 10 4

c. Cage and half-cage hydrocarbons io66 . The bicyclo[2 .z .2]octane group 1o 8

a. Bicyclic hydrocarbons io8b. Amines 11 oc. Alcohols i i id. Aldehydes and ketones 11 2e. Carboxylic acids 11 3f. Tricyclic hydrocarbons . Dicyclohexadiene and its derivatives .

11 57 . The bicycle [3 .2 .1 ]octane group 11 7

a. Hydrocarbons 11 7b. Alcohols 11 8c. Carbonyl derivatives 12 0

8 . The bicyclo[3 .2 .2]nonane group 12 1a. Hydrocarbons 122b. Alcohols 122c. Aldehydes and ketones 122d. Carboxylic acids and their derivatives 12 3

9 . The bicyclo [3 .3 .1] nonane group 124a. Hydrocarbons 124b. Alcohols 12 5c. Ketones 12 5d. Carboxylic acids and their derivatives 12 6e. Transannular reactions of bicyclo[3 .3 .r]nonane and related com -

pounds 12 710 . The bicyclo[4 .2 .1]nonane group 12 8

a. Hydrocarbons and halogeno derivatives 12 8b. Alcohols 12 8c. Ketones 12 8

11 . The bicyclo[5 .1 .1]nonane group 12 912 . Polycyclohydrocarbons and their derivatives 129

a. Adamantane ; tricyclo [3 .3 .1 .1 3 , 7 ] decane 129b. Homoadamantane ; tricyclo[4 .3 .1 .1 4 . 8 ]undecane 13 3c. Twistane ; tricyclo[4 .4 .0 .0 3 , 8]decane 1 3 3d. Congressane ; pentacyclo [7 .3 .1 .1 4 , 12 o 2 .'os . 11 ] tetradecane 1 3 4e. Triamantane ; heptacyclo [7 .7 . 1 3 . 15. o1, 12 .02,' .0 4, 18 .08 . 11]octadecane

1 3 5

Chapter 12 . Bicyclic Monoterpenoids and Related Compound s

A . PELTER and (in part) S. H . HARPE R

1 . Introduction 13 62 . The thujane group 13 7

a. Hydrocarbons 1 3 7b. Alcohols 14 1c. Ketones 1 4 5

3 . The carane group 15 0a. Hydrocarbons 150

b. Ketones 1 5 4c. Carboxylic acids 15 7

4 . The Wagner-Meerwein and Nametkin rearrangements 15 95 . The pinane group 166

a. Hydrocarbons 16 6b. Alcohols, aldehydes and ketones 17 6

6 . The santene group x8 7a. Hydrocarbons 18 7b. Ketones, alcohols and carboxylic acids x89c. Tricyclene and isotricyclene 192

7 . The norbornane group 19 3a. Camphene and related compounds 193b. Camphor, epicamphor and related compounds 199

(i) Camphor, 2-oxobornane, 199 - (ii) Substitution products of camphor ,207 [Halogen derivatives of camphor, 208 - Nitro derivatives of camphor ,212 - Camphorsuiphonic acids, 213 - Hydroxycamphors . 216 - Oxo-camphors : bornaiiediones, 218 - Camphorcarboxylic acids, 2231 - (iii)Epicamphor, 3-oxobornane, 22 4

c. Alcohols 22 6d .• Bases of the bornane series 23 2

8 . The norbornane group : fenchone and related compounds 2 3 3a. Ketones and alcohols 23 4b. Hydrocarbons 2 4 3

9 . Absolute configuration of the bicyclic monoterpenes 249

Chapter 13 . The SesTutterpenoids

RHYS BRYAN T

1. Introduction 2562. Hydrocarbons 25 8

a. Acyclic and monocyclic compounds 25 8

(i) Farnesenes, 258 - (ii) Bisabolenes, zingiberenes and curcumenes, 2 59 -(iii) The clemane group, 26 2

b. Bicyclic compounds of bridged cyclohexane types

26 3

(i) The santalenes and related compounds, 263 - (ii) ßergamotene, 26 6

c. Cyclopentylbenzene types 267d. Hydronaphthalene types 268

(i) Cadinenes and related products, 268 - (ii) Eremophilene, eudalene an drelated compounds, 27 3

e. The calarane group 2 7 4f. The azulene group 2 7 7g. The bicyclo[5 .4 .o]undecane group 28 1Is . Macrocyclic types 28 2

(i) I-iumulenes, 282 - (ii) Caryophyllene and related products, 28 4Physical constants of sesgniterpene hydrocarbons 288

By S . H . Harper.

3 . Sesquiterpenoids with an oxygen function 289a. Acyclic and monocarbocyclic compounds 289

(i) From farnesene and related compounds, 289 - (ii) The santalols, 293 -(iii) Elemane derivatives, 295

b. Hydronaphthalene derivatives and related compounds 296

(i) The cadinols, 296 - (ii) Derivatives of eudalene and related compounds ,298 - (iii) Furanoid derivatives, 302 - (iv) Maaliol and related compounds,304 - (v) Eremophilene derivatives, 306 - (vi) Calarane derivatives, 308 -(vii) Drimene derivatives, 31 0

c. Spiro compounds 31 2d. Guaiol and related azulenes 31 4e. Cedrol and related tricyclic compounds 32 5f. Widdrol 32 6g. Patchouli alcohol and related compounds 327h. Macrocyclic types 329i. Valerenic acid and related compounds 33 2Physical constants of sesquiterpenoids with an oxygen function 33 4

4 . Lactones 33 6a. Monocarbocyclic lactones 33 6b. Hydronaphthalene types

33 7(i) Alantolactone and related compounds, 337 - (ii) The santonins andrelated compounds, 340 - (iii) Drimenin and related compounds, 347 - (iv)Lactones related to eremophilane, 349

c. Compounds related to the azulenes 35 0

(i) Guaianolides, 350 - (ii) Costus lactones and related compounds, 351 -(iii) Abnormal guaianolides, 35 5

d. Macrocarbocyclic lactones ; germacranolides 362Physical constants of sesquiterpenoid lactones 36 6

Chapter 14 . The Diterpenoids, Sesterterpenoids and Triterpenoids

R . MCCRINDLE And K. H . OVERTO N

I . Introduction 369a. General 369b. The Biogenic Isoprene Rule 37 0

2 . Diterpenoids 373a. Bicyclic diterpenoids 37 5

(i) Unrearranged labdanes, 375 - (ii) Rearranged labdanes, 37 7b. Tricyclic diterpenoids 377

(i) Unrearranged pimaranes, 377 - (ii) Rearranged pimaranes, 378 - (iii)The abietane group, 37 8

c. Tetracyclic diterpenoids 37 9(i) The kaurane group, 379 - (ii) The stachane and trachylobane groups, 38 1- (iii) The atisirane group, 381 - (iv) The cembrane group, 38 1

Tables of physical constants 382

3 . Sesterterpenoids 40 3Tables of physical constants 40 5

4 . Triterpenoids 406a. Cyclisation of all-trans squalene in the chair-boat-chair-boat sequence 40 6b. Cyclisation of all-trans squalene in the chair-chair-chair-boat

sequence 409

(i) Group A, 409 - (ii) Group B, 41 2

c. Cyclisation of all-trans squalene in the chair-chair-chair-chair-chai rsequence 41 7

d. Cyclisation of all-trans squalene in the chair-chair-chair-chair-boatsequence 417

e. Cyclisation of all-trans squalene in the chair-boat-chair-chair-boatsequence 41 8

f. Cyclisation of squalene simultaneously from both ends 41 8Tables of physical constants 420

5 . Biosynthesis 46oa. Diterpenoids 46o

(i) Rosenonolactone, 46o - (ii) Gibberellic acid, 461, - (iii) Mutilin, 46 3

b. Sesterterpenoids 463c. Triterpenoids 464

(i) Lanosterol, 464 - (ii) Soyasapogenol D and lupeol, 466 - (iii) Eburicoi cacid, 467

6 . Laboratory synthesis 46 8a. Diterpenoids 46 8

(i) Phytol, 468 - (ii) Sclareol, manool and labdanolic acid, 468 - (iii) De-hydroabietic acid, 469 - (iv) The (±)-pimaradienes and (+)-hibaene, 46 9- (v) Diterpene alkaloids, 47 o

b. Triterpenoids 47 1(i) Squalene, 471 - (ii) Lanosterol and its congeners, 473 - (iii) Cycloartane ,473 - (iv) Onocerin and its congeners, 473 - (v) Olean-1r,13(18)-diene, 47 5- (vi) Conversion of ß-amyrin into multiflorenol, 47 5

7 . Physical methods in the determination of structure and configuration i nnatural products 477

a. Nuclear magnetic resonance 477b. Mass spectrometry 47 8c. Optical rotatory dispersion and circular dichroism 479d. Infrared and ultraviolet spectroscopy 479e. Dissociation constants 48 of. X-ray crystallography 48 o

INDEX 482

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