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 VII OFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS X V LIST 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 nomenclature a. Classification I b. Nomenclature 2 (i) Ring-systems joined directly or through a carbon chain, 3 - (ii) Spir o compounds, 3 - (iii) Fused and bridged ring-systems, 4 2 . Compounds with rings joined directly or through a carbon chain 5 a. General methods of synthesis 6 b. Polycyclopropyl compounds 6 c. Polycyclobutyl compounds 9 d. Polycyclopentyl compounds 9 e. Cyclopropylcyclopentane compounds 1 3 f. Cyclopropylcyclohexane compounds 1 3 g. Cyclobutylcyclohexane compounds 13 h. Cyclopentylcyclohexane compounds 14 i. Polycyclohexyl compounds 1 4 (i) Hydrocarbons, r4 - (ii) Hydroxy and amino derivatives, 15 - (iii) Ketones, 16 - (iv) Carboxylic acids, I q j. Cyclopentylcycloheptane compounds 1 7 k. Cyclohexylcycloheptane compounds 1 8 1. Bicycloheptyl and its derivatives 1 8 m . Bicyclo-octyl and related compounds 1 8 3. Spiro compounds ; spiranes 20 a. The spiro[z .z]pentane group 2 1 b. The spiro[2 .3]hexane group 22 c. The spiro[z .4]heptane group 23 d. The spiro[2 .5]octane group 24 e. The spiro[2,6]nonane group 2 5 f. The spiro[3 .3]heptane group 2 5 g. The spiro[3 .4]octane group 26 h. The spiro[3 .5]nonane group 26 i. The spir0[4 .4]nolla1le group 27 j. The spiro[4 .5]decane group 29 k. The spiro15 .5]undecane group 30 1 . The spiro[5 .6]dodecane group 31 m .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 2 2. The bicyclo[2 .1 .o]pentane group 35 3. The bicyclo[3 .1 .o]hexane group 36 4. The bicyclo[4 .I .o]heptane group 38 5. The bicyclo[S.I .o]octane group 39 6. The bicyclo[6.I.o]nonane group 41 7 . The bicyclo[7 .r .o]decane group 42 8. Bicyclo[2 .2 .o]hexane and related compounds 42 a. Bicyclo[z .2 .o]hexane and its derivatives 42 b. Compounds related to tricyclo[4 .2 .o .o 2 .6 ]octane 43 c. Cubane and its derivatives 44 d. Derivatives of prismane 45 9. The bicyclo[3 .2 .o]heptane group 45 1o . The bicyclo[4 .2 .o]octane group 47 11 . The bicyclo[5 .2 .o] nonane group 5o 12 . The bicyclo[6.2 .o]decane group 50 13 . The bicyclo[3 .3 .o]octane (pentalane) group 3 1 14 . The bicyclo[4 .3 .o]nonane (hydrindane) group 55 15 . The bicyclo15 .3 .o]decane group 59 16 . The bicyclo[4 .4 .o]decane (decalin) group 6o a. Saturated compounds 62 b. Unsaturated compounds 68 17 . The bicyclo[5 .4 .o]undecane group 72 18 . The bicycio[5 .5 .o]dodccane group 72 19 . The bicyclo[6 .6.o]tetradecane group 73 2o . Highly condensed alicyclic systems 73 Chapter I I . Polycarbocyclic Bridged Ring Compounds J. D. LITTLEHAILE S 1. Introduction 77 a. Synthesis and general properties of bridged ring compounds 78 b. Bridged carbonium ions 8o 2 . The bicyclo [I .I .I] pentane group 84 3 . The bicyclo[2 .I .I]hexane group 84 4. The bicycloheptane group 88 a. The bicyclo[3 .I .I]heptane group 8 8 b. The bicyclo[2 .2 .I]heptane (norbornane) group 89 (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 99 a. Polymerisation products of cyclopentadiene 99 b. Perhydrodimethanonaphthalenes (dimethylenedecalins) and thei r derivatives 10 4 c. Cage and half-cage hydrocarbons io6 6. The bicyclo[2 .z.2]octane group 1o 8 a. Bicyclic hydrocarbons io8 b. Amines 11 o c. Alcohols i i i d. Aldehydes and ketones 11 2 e. Carboxylic acids 11 3 f. Tricyclic hydrocarbons . Dicyclohexadiene and its derivatives . 11 5 7. The bicycle [3 .2 .1 ]octane group 11 7 a. Hydrocarbons 11 7 b. Alcohols 11 8 c. Carbonyl derivatives 120 8 . The bicyclo[3 .2 .2]nonane group 12 1 a. Hydrocarbons 122 b. Alcohols 122 c. Aldehydes and ketones 122 d. Carboxylic acids and their derivatives 12 3 9. The bicyclo [3 .3 .1] nonane group 124 a. Hydrocarbons 124 b. Alcohols 12 5 c. Ketones 12 5 d. Carboxylic acids and their derivatives 12 6 e. Transannular reactions of bicyclo[3 .3 .r]nonane and related com - pounds 12 7 10 . The bicyclo[4 .2 .1]nonane group 12 8 a. Hydrocarbons and halogeno derivatives 12 8 b. Alcohols 12 8 c. Ketones 12 8 11 . The bicyclo[5 .1 .1]nonane group 12 9 12 . Polycyclohydrocarbons and their derivatives 129 a. Adamantane ; tricyclo [3 .3 .1 .1 3 , 7 ] decane 129 b. Homoadamantane ; tricyclo[4 .3 .1 .1 4 . 8 ]undecane 13 3 c. Twistane ; tricyclo[4 .4 .0 .0 3 , 8]decane 1 3 3 d. Congressane ; pentacyclo [7 .3 .1 .1 4 , 12 o 2 .'os. 11 ] tetradecane 1 34 e. Triamantane ; heptacyclo [7 .7 . 1 3 . 15.o1, 12 .0 2,'.0 4, 18 .08 . 11]octadecane 135 Chapter 12 . Bicyclic Monoterpenoids and Related Compound s A. PELTER and (in part) S. H. HARPER 1 . Introduction 13 6 2 . The thujane group 13 7 a. Hydrocarbons 137 b. Alcohols 14 1 c. Ketones 145 3. The carane group 150 a. Hydrocarbons 150 b. Ketones 1 54 c. Carboxylic acids 15 7 4. The Wagner-Meerwein and Nametkin rearrangements 15 9 5. The pinane group 166 a. Hydrocarbons 16 6 b. Alcohols, aldehydes and ketones 17 6 6. The santene group x8 7 a. Hydrocarbons 18 7 b. Ketones, alcohols and carboxylic acids x8 9 c. Tricyclene and isotricyclene 192 7. The norbornane group 19 3 a. Camphene and related compounds 193 b. 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 6 d .• Bases of the bornane series 23 2 8. The norbornane group : fenchone and related compounds 233 a. Ketones and alcohols 23 4 b. Hydrocarbons 243 9. Absolute configuration of the bicyclic monoterpenes 249 Chapter 13. The SesTutterpenoids RHYS BRYAN T 1. Introduction 256 2. Hydrocarbons 25 8 a. Acyclic and monocyclic compounds 25 8 (i) Farnesenes, 258 - (ii) Bisabolenes, zingiberenes and curcumenes, 259 - (iii) The clemane group, 26 2 b. Bicyclic compounds of bridged cyclohexane types 263 (i) The santalenes and related compounds, 263 - (ii) ßergamotene, 26 6 c. Cyclopentylbenzene types 267 d. Hydronaphthalene types 268 (i) Cadinenes and related products, 268 - (ii) Eremophilene, eudalene an d related compounds, 27 3 e. The calarane group 2 74 f. The azulene group 277 g. The bicyclo[5 .4 .o]undecane group 281 Is . Macrocyclic types 28 2 (i) I-iumulenes, 282 - (ii) Caryophyllene and related products, 28 4 Physical constants of sesgniterpene hydrocarbons 288 By S . H . Harper. 3 . Sesquiterpenoids with an oxygen function 289 a. 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 2 d. Guaiol and related azulenes 31 4 e. Cedrol and related tricyclic compounds 32 5 f. Widdrol 32 6 g. Patchouli alcohol and related compounds 327 h. Macrocyclic types 329 i. Valerenic acid and related compounds 33 2 Physical constants of sesquiterpenoids with an oxygen function 33 4 4. Lactones 33 6 a. Monocarbocyclic lactones 33 6 b. Hydronaphthalene types 33 7 (i) Alantolactone and related compounds, 337 - (ii) The santonins and related 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 362 Physical constants of sesquiterpenoid lactones 36 6 Chapter 14 . The Diterpenoids, Sesterterpenoids and Triterpenoids R . MCCRINDLE And K . H . OVERTON I. Introduction 369 a. General 369 b. The Biogenic Isoprene Rule 37 0 2. Diterpenoids 373 a. Bicyclic diterpenoids 37 5 (i) Unrearranged labdanes, 375 - (ii) Rearranged labdanes, 37 7 b. 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 403 Tables of physical constants 405 4. Triterpenoids 406 a. Cyclisation of all-trans squalene in the chair-boat-chair-boat sequence 40 6 b. Cyclisation of all-trans squalene in the chair-chair-chair-boa t sequence 409 (i) Group A, 409 - (ii) Group B, 41 2 c. Cyclisation of all-trans squalene in the chair-chair-chair-chair-chai r sequence 41 7 d.