RODD'S CHEMISTR Y

OF CARBON COMPOUND S

A modern comprehensive treatise

SECOND EDITIO N

Edited by

S . COFFEY

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

LC.I. Dyestuffs Division, Blackley, Manchester

VOLUME III PART H

AROMATIC COMPOUND S

Polycarbocyclic compounds with more than thirteen atoms in the fused-rin g

system

CUMULATIVE INDEX VOL . III PARTS A - H

VOLUME III H

Aromatic Compounds: Polycarbocyclic compounds with more than thirteen atoms i nthe fused-ring system . Cumulative Index to Vol . III A - H

LPREFACE VII

OFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS XIV

LIST OF ABBREVIATED NAMES OF CHEMICAL FIRMS MENTIONED IN PATENT REFERENCES

XV

LIST OF COMMON ABBREVIATIONS AND SYMBOLS USED XVI

Chapter 28. Aromatic Compounds with Three Fused Carbocyclic Ring Systems :Anthracene, Phenanthrene and Related Compounds

by MALCOLM SAINSBUR Y

Introduction 1Structure 2Stereochemistry of 9,10-dihydro-anthracenes and -phenanthrenes 5

1 . Anthracene and its derivatives 5a. Anthracene 5

(i) Methods of formation and synthesis, 5 - (ii) Properties and reactions, 8 -

b. 9,10-Dehydroanthracene 2 5c. Homologues of anthracene 25

(i) Preparation, 28 - (ii) Properties . 30 -

d. Aminoanthracenes (anthrylamines) 3 0e. Hydroxyanthracenes (anthrols) 32

(i) Preparation, 32 -

f. Anthracenecarboxylic acids and their functional derivatives 40

2. Anthraquinones and related compounds 4 1a. 1,2-Anthraquinone 41b. 1,4-Anthraquinone 42c. 1,5- and 2,6-Anthraquinones 45d. 9,10-Anthraquinones and their derivatives 45

(i) Methods of formation, 46 - (ii) Physical properties and reactions of 9,10 -anthraquinone, 49 - (iii) Homologues of anthraquinone, 57 - (iv) Halogeno-anthraquinones, 58 - (v) Nitroanthraquinones, 60 - (vi) Anthraquinone-sulphonic acids, 62 - (vii) Hydroxyanthraquinones, 63 - (viii) Naturally occurringanthraquinones, 73 - (ix) Aminoanthraquinones, 82 - (x) Acylanthraquinones,88 - (xi) Anthraquinonecarboxylic acids, 90 -

e. Anthradiquinones 9 1

3 . Bianthryls and their derivatives 9 4a. Bianthryls 94

CO 1,1'- and 2,2'-Bianthryls, 94 - (ii) meso-Bianthryls, 95 - (iii) Bianthrols an dbianthrones, 97 -

b. Bianthraquinones 9 8

(i) 1,1'- and 2,2'-Bianthraquinones, 98 - (ii) Bianthryl-9,10 :9',10'-diquinones ,99 - (iii) Naturally occurring bianthraquinones, 101 - (iv) Extended bianthryl-quinones, 103 -

4 . Phenanthrene and its derivatives 104a. Phenanthrene

10 4(i) Methods of synthesis, 104 - (ii) Properties and reactions, 114 -

b. Homologues of phenanthrene 12 1c. Aminophenanthrenes or phenanthrylamines 12 3d. Hydroxyphenanthrenes or phenanthrols

124(i) Phenanthrols and their derivatives, 124 - (ii) Phenanthrenediols, 126 - (iii)Phenanthrene-triols and -tetra-ols, 128 -

e. Naturally occurring phenanthrenes and dihydrophenanthrenes 12 8f. Formyl- and acyl-phenanthrenes 13 1g. Phenanthrenecarboxylic acids 13 1h. Phenanthrenequinones 133i. Biphenanthryls 136

Chapter 29 . Fused-Ring Polycyclic Aromatic CompoundsContaining One or More Five-Membered Rings, p . 137

by H. F . ANDRE W

1 . The benzindan group 138a. Benzindans and related compounds 138

2 . The acenaphthene group 140a. Acenaphthene

140(i) Reactions, 140 -

b. Acenaphthene derivatives

145Tautomeric form of acenaphthene, 146 -

c. Acenaphthylene 147(i) Synthesis, 147 - (ii) Reactions, 148 - (iii) Homologues and their derivatives ,150 -

d. Benzologues of acenaphthene 15 0e. Related hydrocarbons 151

3. The fluorene group 15 2a. Fluorene

15 2(i) Structure, 153 - (ii) Methods of formation, 154 - (iii) Properties, 158 -

b. Chemical reactions of fluorene 15 8(i) Oxidation, 158 - (ii) Hydrogenation of fluorene, 158 - (iii) Addition reaction ,160 - (iv) Reactions at the 9-position, 160 - (v) Fluorenylidene derivatives 161 -(vi) Electrophilic substitution, 162 - (vii) Free-radical substitution : 9-substitute dfluorenes, 168 - (viii) Fluorenone and its derivatives, 171 -

c. Bifluorenes and trifluorenes 17 5d. Benzofluorenes 17 7

(i) Monobenzofluorenes, 177 - (ii) Dibenzofluorenes, 182 - (iii) Higher annelate dfluorenes, 183 - (iv) Natural products of the fluorene group . 183 -

4 . The fluoranthene group 18 4a. Fluoranthene and its derivatives 18 4

(i) Methods of formation, 185 - (ii) Properties, 188 -

b. Chemical reactions of fluoranthene 18 9

(i) Oxidation, 189 - (ii) Electrophilic substitution, 189 - (iii) Nucleophilicsubstitution, 193 -

c. Hydrogenated fluoranthenes 19 3d. Methyl- and phenyl-fluoranthenes 19 5e. Benzofluoranthenes 19 5f. Natural products of the fluoranthene group 197

5 . Hydrocarbons containing two five-membered rings 198a. The benzindan group

198s-Indacene and as-indacene, 198 -

b. The acenaphthene group

200Pyracene and pyracylene, 200 -

e. The fluorene group

202(i) Fluorenacenes and fluorenaphenes, 202 - (ii) Dibenzopentalenes and relatedcompounds, 203 -

d . The fluoranthene group 20 5

6. Hydrocarbons containing 5- and 7-membered rings 20 6a . Cyclohept[fg]acenaphthylene 20 6b . Acepleiadylene and acepleiadene 20 6c . Benzazulenes 207

Chapter 30 . Polycyclic Aromatic Compounds with Four or More(usually six-membered) Fused Carbocyclic Ring Systems

by N. CAMPBELL AND H . F. ANDRE W

1 . Introduction and general properties 21 1a. Definition 21 1b. Nomenclature 21 2c. General physical properties

21 3(i) Bond length and bond orders, 213 - (ii) Molecular planarity ; molecular over-crowding ; helicenes, 214 - (iii) Ultraviolet spectra, 216 - (iv) Nuclear magneti cresonance, 218 - (v) Diamagnetic susceptibility, 218 - (vi) Resonance energy ,219 - (vii) Proton addition . Complexes and ions, 221 -

d. General chemical properties

22 1(i) Addition reactions, 221 - (ii) Electrophilic substitution, 224 - (iii) Oxidation ,225 - (iv) Molecular rearrangements, 226 - (v) Charge-transfer complexes, 227 -(vi) Colour tests, 227 -

e. Methods of preparation

22 8(i) Cyclic dehydrogenation, 229 - (ii) Photo-oxidative ring-closure, 230 - (iii) Elbssynthesis, 231 - (iv) Synthetic uses of acid anhydrides, 233 - (v) Cyclisatio nwith loss of hydrogen bromide, 234 - (vi) Ring-formation by neighbouringgroup interaction, 235 - (vii) Syntheses involving naphthyne and similar inter -mediates, 236 - (viii) Addition of 2-carbon and 3-carbon fragments to aromati chydrocarbons, 237 - (ix) Molecular rearrangement, 237 -

2. Individual hydrocarbons containing four benzene rings 23 8a . Chrysene and its derivatives

23 8(1) Syntheses, 238 - (ii) Reactions, 241 -- (iii) Alkylchrysenes, 243 - (iv) Hydro-chrysenes, 243 -

b. Naphthacene, tetracene, benz[b]anthracene ; rubrene 245

(i) Synthesis, 245 - (ii) Reactions, 246 - (iii) Antibiotics derived from naphtha-cene, 249 -

c. Benz[a]anthracene, 1,2-benzanthracene, tetraphene 25 1(i) Synthesis, 251 - (ii) Reactions . 252 - (iii) Alkylbenz[a]anthracenes, 254 -(iv) Hydrobenz[a]anthracenes, 255 -

d. Benzanthracenes and their derivatives 25 6(i) Preparation and synthesis, 257 - (ii) Reactions, 258 - (iii) Arylbenzanthrones ,260 - (iv) Isomeric benzanthrenes, 261 - (v) Dibenzanthrones ; violanthrone ,dibenzanthrone, 261 -

e. Pyrene and its derivatives

264

(i) Synthesis, 265 - (ii) Reactions, 266 - (iii) Hydropyrenes, 270 -f. Triphenylene and its derivatives

272(i) Triphenylene, 272 - (ii) Hydrotriphenylenes, 274 -

g. Pleiadene, benzocyclohepta[de]naphthalene 275

3 . Hydrocarbons containing five benzene rings 27 6a. Pentacene, lin-dibenzanthracene, benzo[b]naphthacene 27 6

(i) Synthesis, 276 - (ii) Reactions, 277 -

b. Pentaphene, 2,3-6,7-dibenzophenanthrene 27 8c. Benzo[a]naphthacene, 1,2-benzotetracene 279d. Dibenzanthracenes 280

(i) Dibenz[a,c]anthracene, 280 - (ii) Dibenz[a,i]anthracene, 1,2-7,8-dibenz-anthracene, 281 - (id) Dibenz[a,h]anthracene, 1,2-5,6-dibenzanthracene, 281 -

e. Benzochrysenes 28 3

(i) Picene, 1,2-7,8-dibenzophenanthrene, benzo[a]chrysene, 283 - (ii) Benzo[b] -chrysene, 1,2-6,7-dibenzophenanthrene, 285 - (iii) Benzo[c]chrysene, 1,2-5,6 -dibenzophenanthrene,28( (iv) Benzo[a]chrysene,1,2-3,4-dibenzophenanthrene ,286 -

f. Dibenzophenanthrene 28 7g. Benzopyrenes 28 8

(i) Benzo[a]pyrene, benzo[def]chrysene, 1,2-benzopyrene, 3,4-benzopyrene ,288 - (ii) Benzo[e]pyrene, 4,5-benzopyrene, 1,2-benzopyrene, 290 - (iii) Benzo-[c,dlpyrene, naphthanthrene, 291 -

h. Perylene and its derivatives 292(i) Perylene, 292 - (ii) Perylenequinones, 295 - (iii) Hydroperylenes, 296 - (iv)Aphins, 297 - (v) Elsinoe pigments, 297 -

i. Triptycene, 9,10-dihydro-9,10-o-benzenoanthracene 298

4 . Hydrocarbons containing six or more benzene rings 300a. Hydrocarbons with six rings 300b. Hydrocarbons with seven or more rings 307

Cumulative Index to Volumes III A-Ill H 313