Supplements to the 2nd Edition (Editor S. Coffey) of RODD'S CHEMISTRY O F CARBON COMPOUND S A modern comprehensive treatise Edited by M. F. ANSELL Ph.D., D.Sc. (London), F.R.I.C. Department of Chemistry, Queen Mary College , University of London (Great Britain) Supplement t o VOLUME II ALICYCLIC COMPOUND S Part A : Monocarböcyclic compounds to and including five ring atom s Part B: Six- and higher-membered monocyclic compounds VOLUME II A B Alicyclic Compounds ; Monocarbocyclic Compounds to and including Five Rings Atoms ; Six- and Higher-Membered Monocyclic Compounds . Preface vi i Official publications ; Scientific Journals and periodicals xiv List of common abbreviations and symbols used x v Chapter 1 . Introductio n by MARTIN F . ANSEL L 1 . Pericyclic reactions . 1 a. Generalised Woodward-Hoffmann rule for pericyclic reaction . 6 b. Theoretical basis of Woodward-Hoffmann rules . 7 2 . Stereochemistry and conformational analysis 8 Chapter 2 . The Cyclopropane Group by P . H . BOYL E 1 . Preparative methods 9 a. Methods based on 1,3-cyclisation 9 b. Methods based on ring contraction . 1 2 c. Methods based on carbene addition . 1 4 (i) Halocarbenes, 14 - (ii) Other carbenoid reactions, 16 - 2 . Saturated hydrocarbons . 1 8 3 . Unsaturated hydrocarbons . 2 0 4 . Halogen derivatives of cyclopropane 2 7 5 . Organometallic compounds derived from cyclopropanes 3 0 6 . Alcohols derived from cyclopropanes 3 1 7 . Sulphur derivatives of cyclopropanes 3 3 8 . Nitrocyclopropanes . 3 4 9 . Amines and related compounds derived from cyclopropanes . 3 4 10 . Aldehydes and ketones derived from cyclopropanes 3 6 11 . Cyclopropane- and cyclopropene-carboxylic acids 4 3 12 . Cyclopropyl and cyclopropenyl carbanions 44 13 . Cyclopropyl radicals _ 4 5 14 . Natural products containing a cyclopropyl ring . 46 Chapter 3 . The Cyclobutane Group by IAN FLEMIN G 1 . Occurrence, formation and general properties . 49 a. Syntheses and preparative methods 49 b. General properties of cyclobutanes . 5 7 2 . Natural products containing a cyclobutane ring _ 5 9 Chapter 4 . The Cyclopentane Group by P . W . HICKMOTT 1 . Synthesis and spatial geometry of cyclopentane compounds . 6 1 a. Preparative methods . 6 1 (i) Ring-contraction, 61 - (ii) Ring-expansion, 64 - (iii) Miscellaneou s cyclizations, 65 - b. Conformational analysis 6 6 2 . Hydrocarbons 6 8 a. Saturated hydrocarbons 6 8 b. Mono-unsaturated hydrocarbons 6 8 (i) Cyclopentenes, 68 - (ii) Hydrocarbons with unsaturated side chains , 70 - (iii) Cyclopentyne, 72 - c. Poly-unsaturated hydrocarbons 7 2 (i) Cyclopentadiene, 72 - (ii) Alkyl- and aryl-cyclopentadienes, 73 - (iii) Cyclopentadienyl ions and radicals, 74 - (iv) Fulvenes and ful- valenes, 77 - 3 . Metal cyclopentadienyls ; metallocenes 8 1 a. Synthesis 8 2 b. Chemical properties 8 4 (i) Electrophilic substitution, 84 - (ii) Nucleophilic addition and sub- stitution, 86 - (iii) Reduction and oxidation, 88 - (iv) Ligand exchange and insertion, 89 - (v) Stability and reactions of the a- metallocenyl carbonium ion, 94 - (vi) Bridged ferrocenes, ferroceno- phanes, 96 - (vii) Bi- and poly-ferrocenes, 98 - (viii) Di- and poly - nuclear complexes, 99 - (ix) Carboranes, 101 - c. Physical properties and structure of cyclopentadienyl metal compounds 102 (i) Structure and fluxional behaviour, 102 - (ii) Stereochemistry, 10 6 - (iii) Spectroscopic properties, 107 - d. Orbital symmetry considerations 10 7 4. Halogen derivatives . 108 5 . Nitro and amino derivatives 11 1 6 . Alcohols of the cyclopentane and cyclopentene series . 11 2 a. Secondary and tertiary cyclopentanols 11 2 b. Cyclopentanediols - 11 3 c. Unsaturated cyclopentanols 11 4 d. Cyclopentanepentols 11 4 7 . Aldehydes _ 11 5 8 . Ketones 11 7 a. Ring ketones 11 7 (i) Saturated monoketones, 117 - (ii), Unsaturated monoketones, 118 - 9 . Hydroxyketones and polyketones of the cyclopentene series . 12 3 a. Hydroxycyclopentenones ; cyclopentenolones . 12 3 (i) Pyrethrins, rethrolones, and rethrones, 123 - (ii) "Anhydroacetone- benzils" , 125 - b. Ring-polyketones 12 6 (i) 1,2-Diketones, 126 - (ii) 1,3-Diketones, 126 - c. Poly- and exo-cyclic ketones . 12 8 10 . Carboxylic acids, amides and esters 13 0 a. Saturated monocarboxylic acids 13 0 b. Unsaturated monocarboxylic acids and derivatives 13 0 c. Polycarboxylic acids . 13 2 d. Keto-acids 13 3 e. Prostaglandins . 13 5 Chapter 5 . The Cyclohexane Group by A. J . BELLAM Y 1 . Formation and properties . 14 3 a . Methods of formation . 14 3 (i) Cyclohexenes, 150 - (ii) Alkylidene- and alkenyl-cyclohexanes, 15 3 - (iii) Cyclohexadienes, 154 - (iv) Alkylidene- and alkenyl-cyclo- b . hexenes, 156 - 14 5 2 . Hydrocarbons 14 9 a. Saturated hydrocarbons: Cyclohexanes 14 9 b. Unsaturated hydrocarbons . 15 0 (i) Cyclohexenes, 150 - (ii) Alkylidene- and alkenyl-cyclohexanes, 15 3 - (iii) Cyclohexadienes, 154 - (iv) Alkylidene- and alkenyl-cyclo- hexenes, 156 - 3 . Halogeno derivatives of the hydrocarbons 15 6 4 . Alcohols and their derivatives 15 7 a. Alcohols 15 7 (i) Monohydric alcohols, 157 - (ii) Dihydric and trihydric alcohols , 158 - (iii) Polyhydric alcohols (tetrols, pentols, and hexols), 159 - b. Epoxycyclohexanes . 16 0 c. Peroxides 16 1 5 . Nitro- and amino-cyclohexanes 16 1 a. Nitro compounds 16 1 b. Amines . 16 1 6 . Alicyclic aldehydes 16 2 7 . Alicyclic ketones 16 3 a. Saturated ring ketones 1b 3 (i) Cyclohexanones, 163 - (ii) Cyclohexanediones, 166 - b. Unsaturated ring ketones . 16 7 c. Exocyclic unsaturated ring ketones . 17 0 d. Exocyclic ketones 17 0 8 . Carboxylic acids 17 1 (i) Cyclohexanecarboxylic acids, 171 - (ii) Unsaturated carboxylic acids, 172 - (iii) Exocyclic carboxylic acids, 172 - (iv) Hydroxycar- boxylic acids, 172 - (v) Aminocarboxylic acids, 173 - Chapter 6. The Acyclic and Mono cyclic Mono terpenoids by S . H . HARPE R 1. Introduction 17 5 2. Acyclic monoterpenoids 17 5 3. Monocyclic monoterpenoids 17 9 a. Tetramethylcyclohexane derivatives 17 9 b. p-Menthane derivatives 18 2 C . o-Menthane derivatives 18 3 d. Cyclopentane derivatives 18 4 e. Other monocyclic monoterpenoids 18 9 Chapter 7. The Carotenoid Group by J . B . DAVI S 1 . Basic constitution, classification, and nomenclature 19 2 2 . Occurrence, function and isolation 19 5 3 . Structure and synthesis 19 9 4 . Properties of carotenoids 20 1 a. General properties ; cis-trans isomerism 20 1 b. Physical properties 20 3 (i) Visible and ultraviolet absorption spectra, 203 - (ii) Infrare d spectra, 204 - (iii) Nuclear magnetic resonance, 204 - (iv) Mas s spectrometry, 208 - (v) Optical rotatory dispersion (o .r.d .) an d circular dichroism (c .d), 210 - (vi) Resonance-enhanced Raman (r .e .r . ) spectroscopy, 212 - C . Chemical properties 21 3 (i) Oxidative cleavage at the central double bond of p-carotene (an d ring-substituted 0-carotenes) to give retinal (and substituted retinals) , 213 - (ii) Reaction with N-bromosuccinimide (NBS), 213 - (iii) Reaction with titanium tetrachloride, 213 - (iv) Reactions of caro- tenoids containing allylic hydroxyl (or alkoxyl) groups, 215 - 5 . Carotenoid hydrocarbons 21 7 6 . The vitamins A and related compounds 22 5 a. Vitamin A 1 : retinol 22 5 (i) The conversion of carotenoids into retinol, 225 - (ii) Synthesis o f retinol (vitamin A) and related compounds, 227 - b. Vitamin A 2 : 3,4-dehydroretinol 22 8 C . Retinal and 3,4-dehydroretinal, and the visual process 22 8 The visual process, 229 - (A) Properties of rhodopsin : The nature o f the retinal-opsin link, 232 - (B) The position of the absorption maxi - mum in rhodopsin and prelumirhodopsin, etc ., 235 - (C) The nature of the opsin part of the rhodopsin molecule, 238 - The bleachin g process in vivo ; the final step in the bleaching process; the retinal cycle , 240 - The visual process in other species, 241 - d. Kitol 24 1 e. Properties of the vitamins A and related compounds 242 (i) Physical properties, 242 - (ii) Chemical properties, 242 - 7 . Carotenoid compounds containing oxygen ("xanthophylls") 24 5 a. Carotenoid epoxides : general properties 24 5 b. Cyclic hydroxycarotenoids and their oxides, and the hydrocarbo n oxides . 24 9 c. Acyclic hydroxy-, methoxy-, and methoxy oxo-carotenoids 26 3 d. Aldehydo-, keto-, and hydroxyketo-carotenoids . 26 6 (i) Aldehydes and hydroxyaldehydes, 266 - (ii) Keto- and hydroxy- keto-carotenoids, 270 - e. Carotenoid carboxylic acids . 28 4 f. Allenic carotenoids 288 g. Acetylenic carotenoids 300 h. C 50 (and C45 ) carotenoids 309 i. Carotenoids with partially oxidised methyl groups 320 j. Nor-carotenoids : C3 8 and allied compounds 327 k. Aryl carotenoids . 330 I . Carotenoids of uncertain constitution 33 2 8 . The biosynthesis of carotenoids 33 5 a. Biosynthesis of hydrocarbons 33 5 (i) General, 335 - (ii) The conversion of mevalonic acid into phytoen e and lycopene, 337 - (iii) The cyclisation step, 350 - b. Biosynthesis of xanthophylls . 35 5 (i) The insertion of oxygen functions, 355 - (ii) Me 2 C(OH)•CH 2 ••• - > Me 2 C(OMe)•CH 2 •••, 357 - (iii) Miscellaneous postulated pathways , 357 - Chapter 8 . The Cycloheptane, Cyclo-octane and Macro cyclic Group s by S . H_ GRAHA M 1 . Cycloheptane group . 35 9 a. Hydrocarbons . 35 9 b. Alcohols 36 1 c. Ketones . 36 1 d. Carboxylic acids 36 1 2 . Tropylium salts, tropone 36 1 a. Tropylium salts 36 2 b. Tropone 36 2 c. Tropolones 36 3 d. Rearrangements of tropones . 364 e. Photochemistry of tropolones 36 5 f. Thia analogues of tropolone . '36 6 3 . Macrocyclic compounds 36 6 a. Hydrocarbons . 36 6 (i) Cyclic olefins, 367 - (ii) Annulenes, 371 - b. Functionally substituted macrocycles 37 7 4 . The nonadrides 38 3 5 . Conformations of larger rings 38 5 6 . Catenanes and very large rings 389 Index 391.