Second Supplements to the 2nd Edition of

R ODD' S CHEMISTRY OF

CARBON COMPOUNDS

A modern comprehensive treatis e

Edited byMALCOLM SAINSBURY

School of Chemistry, The University of Bath,Claverton Down, Bath BA2 TAY,, England

Second Supplement to

VOLUME III AROMATIC COMPOUND S

Part F: Polybenzenoid Hydrocarbons and their Derivatives :Hydrocarbon Ring Assemblies, Polyphenyl-substituted

Aliphatic Hydrocarbons and their Derivative s(Partial : Chapter 24 in this Volume)

Part G: Monocarboxylic Acids of the Benzene Series : C,-C 13 -carbocyclic Compounds with Fused-ring System s

and their DerivativesPart H: Polycarbocyclic Compounds with more than Thirteen

Atoms in the Fused-ring System

Volume III F(partial), G and H

Aromatic Compounds: Polybenzenoid Hydrocarbons and their Derivatives ; Hydrocar-bon Ring Assemblies, Polyphenyl-substituted Aliphatic Hydrocarbons and their Deriva-tives (partial )Monocarboxylic Acids of the Benzene Series : C,-C,3-carbocyclic Compounds with Fused -ring Systems and their DerivativesPolycarbocyclic Compounds with more than Thirteen Atoms in the Fused-ring Syste m

List of contributors viPreface viiList of common abbreviations and symbols used xy

Chapter 24. Bis- and Tris-(phenylalkyl)benzenes and LinearOligo(phenylenealkyl)s, their Derivatives and Oxidation Product s

by J.M. MELLO R

1 . Introduction 12 . Cyclophanes 1

(a) (n)Cyclophanes 2(b) (m, n)Paracyclophanes 5(c) (m, n)Metacyclophanes 6(d) Other (m, n)cyclophanes 9(e) Multilayered cyclophanes 1 1(f) Multibridged cyclophanes 1 4(g)(m„)(m,n)Cyclophanes 1 6

3 . Calixarenes 2 04 . Naturally occurring products 2 6

Chapter 25. Monocarboxylic Acids of the Benzene Seriesby M . SAINSBURY

1 . Benzoic acids 3 3(a) Methods of preparation

3 3(i) From arenes, 33 - (ii) From toluenes, 33 - (iii) From aryl halide sby carbonylation, 34 - (iv) From arynes, 34 - (v) From benzyl andphenacyl halides, 35 - (vi) From dienes by cycloaddition reactions, 35 -(vii) From benzaldehydes and related compounds, 40 - (viii) By lithiation-carboxylation, 41 - (ix) Miscellaneous methods, 43 - (x) Isotopicallylabelled benzoic acids, 45-

(b) Reactions

4 6(i) Decarboxylation, 46 - (ii) Reduction to benzaldehydes and benzy lalcohols, 46 - (iii) Reductive dehalogenation, 48 - (iv) Birch reductionand the reactions of dihydrobenzoic acids, 48 - (v) Formation of ketones ,50 - (vi) Nuclear bromination, 50 - (vii) Nuclear hydroxylation, 51 -

2 . Benzoate esters 5 1(a) Preparation

5 1(i) From sodium benzoates and benzoic acids, 51 - (ii) From araldehydes ,53 - (iii) From aromatic nitriles, 53 - (iv) From aryl halides and ary ltrifates, 53 - (v) From coupling reactions, 54 - (vi) From a, Q-diketones ,54 - (vii) Miscellaneous methods, 55 -

(b) Physical properties and reactions

5 9(i) Mass spectra, 59 - (ii) Reduction, 59 - (iii) Alkylation, 61 - (iv )Rearrangements, 62 - (v) Formation of biaryls, 62 - (vi) Oxetan eformation, 65 - (vii) Nucleophilic displacement of nuclear substituents ,66 -

3 . Aroyl halides 67(a) Synthesis

67(i) From aryl halides, 67 - (ii) From benzoic acids, 67 - (iii) Fro mmiscellaneous sources, 67 -

(b) Reactions

6 8(i) Reduction, 68 - (ii) Coupling reactions, 69 - (iii) Insertion reactions ,70 - (iv) Formation of aroylsilanes, 70 -

4 . Aromatic acid anhydrides 7 1(a) Synthesis

7 1(i) From benzoyl halides, 71 - (ii) From benzoic acids, 71 - (iii) Fro marenes, 71 -

5 . Benzamides 7 2(a) Synthesis •

-

7 2(i) From azides, 72 - (ii) From benzonitriles, 72 - (iii) From benzaldehydes ,72 - (iv) From benzoyl halides, 73 - (v) From benzamides and imides ,73 -

(b) Reactions

7 3(i) Ortho-lithiation and related reactions, 73 - (ii) N-Halogenation ,78 - (iii) Reactions with phosphines and the synthesis of enamides an ddienamides, 79 - (iv) Alkylation and the formation of ketones, 79 -(v) Reduction, 80 - (vi) Hydroxylation, 80 - (vii) Coupling reactions, 81 -(viii) Benzamides as nucleophiles, 81- (ix) Pyrolysis, 82 - (x) Spectroscopy ,83 -

6 . Benzonitriles 8 3(a) Synthesis

8 3(i) From benzamides, 84 - (ii) From alkylarenes, 84 - (iii) Fromaraldehydes, aldoximes and hydrazones, 85 - (iv) From aryl iodides ,86 - (v) From benzoic acids and benzoyl halides, 87 - (vi) From alky lthiobenzoates and thiobenzamides, 87 - (vii) By cycloaddition reactions ,87 - (viii) Miscellaneous, 88 -

(b) Reactions

89(i) Hydrolysis, 89 - (ii) Reduction, 89 - (iii) Reactions with azides, 90 -(iv) Formation of N-ebutoxycarbonyl)arylamines, 91 -

7 . Benzonitrile oxides 92

8 . Aroyl cyanides 92

(a) Synthesis

92(i) From aroyl halides, 92 - (ii) From araldehydes, 93 - (iii) Fromarylglyoxals and phenacyl halides, 93 -

(b) Reactions 949 . Aroyl azides 94

(a) Synthesis

94(i) From benzoic acids and benzoyl halides, 94 - (ii) From phenacy ldibromides, 94 - (iii) From aroylhydrazines, 94 -

(b) Reactions

95(i) Reduction, 95 - (ii) Curtius rearrangements to isocyanates, 95 -

10 . Aroyl cyanates 95

11 . N-Aroylhydrazines and aroylazoalkenes 9 512 . Benzimidoyl halides and related compounds 9 613 . Aminobenzoic acids and related compounds 9 7

14 . Thiobenzoic acids, their derivatives, and selenium and tellurium analogues

98

(a) Thiobenzoic acids 98(b) Thiobenozate esters 99

(i) Synthesis, 99 - (ii) Mass spectra, 99 - (iii) Natural product, 99 -

(c) Thiobenzamides 99(i) Synthesis, 99 - (ii) Physical properties and reactions, 100 -

(d) Aroylsulphenyl halides 102(e) Diaroyl disulphides and related compounds 10 2

(f) Dithiobenzoic acids and esters 10 3(g) Seleno- and telluro-benzoic acids 10 3(h) Seleno- and telluro-benzoate esters 10 4(i) Arylcarbonyldiselenides and selenium, or tellurium bis(dithiocarboxylates) 10 4

Chapter 26. Benzocyclopropene, Benzocyclobutene and Indene, and thei rDerivative s

by M.M . COOMB S

1 . Benzocyclopropene and its derivatives 10 5(a) Syntheses of benzocyclopropenes 10 6(b) Reactions involving opening of the cyclopropene ring 10 7(c) Reactions leading to enlargement of the cyclopropene ring 11 2(d) Reactions at the cyclopropene methylene group 11 3(e) Other reactions of benzocyclopropene 11 5

2 . Benzocyclobutene and its derivatives 11 7(a) Syntheses of benzocyclobutene 11 9(b) Reactions involving opening of the four-membered ring 12 5(c) Other reactions of benzocyclobutene 13 1(d) Organometallic derivatives of benzocyclobutene 13 1

3 . Indene and its derivatives 13 3(a) Syntheses of indenes 13 4(b) Syntheses of indanones 136

(c) Reactions at the cyclopentene double bond in indene 13 8(d) Reactions at the benzylic methylene group in indene 14 2(e) Spiro-indenes 14 3(f) Oxidation of indenes 144

Chapter 27. Aromatic Compounds with Condensed Nuclei : Naphthalene an dRelated Compounds

by N .H. WILSON

1 . NaphthaIene 14 72 . Valence isomers of naphthalene 14 83 . General properties of the naphthalene ring system 15 2

(a) Steric effects 15 2(b) Electrophilic substitution reactions

15 5(i) Nitration, 155 - (ii) Acylation, 157 - (iii) Sulphonation, 158 -(iv) Miscellaneous reactions, 159 -

(c) Nucleophilic substitution reactions 16 0(d) Other substitution reactions including metallation and free radical

16 4(i) Lithiation, 164 - (ii) Arylation, 166 -

4 . Didehydronaphthalenes (naphthynes) 16 6(a) 1,2- and 2, 3-Didehydronaphthalenes 167(b) 1, 8-Didehydronaphthalenes 168(c) 1, 4-Didehydronaphthalenes 16 9(d) Other didehydronaphthalenes 17 1

5 . Formation of the naphthalene nucleus 172(a) Cyclisation of benzene derivatives

17 2(i) Aryne mediated ring formation, 172 - (ii) Traditional cyclisatio nmethods, 173 -

(b) Diels-AIder reactions with o-xylylenes (o-quiniodimethanes) 17 3(c) Other Diels-Alder reactions 17 5(d) Other cyclisation reactions 17 7

6 . Reduction and oxidation of naphthalenes 18 0(a) Reduction 18 0(h) Oxidation

18 0(i) Oxidation to quinones, 180 - (ii) Oxidation leading to ring cleav-age or substituent oxidation, 182 - (iii) Naphthalene oxides, naph-thalenols(naphthols) and related compounds, 183 -

7 . Small ring annelated naphthalenes 18 8. . . . . . . . . . . . . . . . . . . . .(a) Naphthocyclobutanes 18 8(b) Naphthocyclopropanes 19 1

8 . Phenalene, phenalenone and related compounds 19 39 . Azulene and related compounds 19 7

(a) Structure and properties of azulene systems 19 7(b) Quinones of azulenes (azuloquinones) 20 0(c) Diels-Alder reactions of azulenes 20 2(d) Valence isomers of azulene 20 3(e) Substitution reactions of azulene

20 5(i) Electrophilic substitution, 205 - (ii) Nucleophilic substitution, 205 -(iii) Other substitution reactions, 206 -

(f) Formation of azulenes 20 610 . Benzocycloheptatrienes, benzotropones, and related compounds 21 0

(a) Formation 21 0(b) Reactions of benzocycloheptatrienes and benzotropones 21 7

11 . Benzocyclooctatetraenes and related compounds 22 0

Chapter 28 . Anthracene, Phenanthrene and Derivative sby R . BOLTON

1. Phenanthrene 22 72. Anthracene and its compounds 23 3

Chapter 29. Polyannular aromatic compounds containing one or morefive-membered rings

by R . BOLTO N

1 . The benzindene group 24 52 . The acenaphthene group 24 6

(a) Acenaphthene and acenaphthylene - reactions 246(b) Aceanthrylene and acephenanthrylene 254(c) Benzaceanthrylenes and benzacephenanthrylenes 25 5

3 . The fluorene group 25 9(a) Fluorene

25 9(i) Synthesis and substitution, 261 - (ii) Derivatives, 265 -

(b) Benzofluorenes 26 84. Cyclopentaphenanthrenes and cyclopentaphenalenes 27 35 . The fluoranthene group 27 5

(a) Fluoranthene 27 5(b) Benzofluoranthenes 27 8

6 . Larger systems containing five-membered rings 28 2

(a) Synthesis 28 2(b) Structures with two or more five-membered rings 28 7(c) Fullerenes 28 9

Chapter 30. Polyannular aromatic compounds containing four or moresix-membered rings

by R . BOLTON

1 . Naphthacene (Tetracene) 29 22 . Chrysene 29 63 . Benz[a]anthracene 29 9

(a) Substituted benz[a]anthracenes 30 2(b) Metabolites of benz[a]anthracene derivatives 30 5

4 . Benz[d,e]anthracene 30 85 . Benzo[c]phenanthrene 31 06 . Pyrene 31 17 . Triphenylene 31 38 . Benzo[g]chrysene 31 59 . Benzopyrenes 31 6

10 . Dibenzanthracenes 320

11. Dibenzophenanthrenes 32 112. Perylene 32413. Dibenzonaphthacenes 32514. Iptycenes 32515. Larger systems 327

Guide to the index 329Index 331