RODD'S CHEMISTR Y

OF CARBON COMPOUND S

A modern comprehensive treatise

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, Mancheste r

VOLUME IV PART F

HETEROCYCLIC COMPOUND S

Six-membered heterocyclic compounds with a single nitrogen atom in th ering ; pyridine, polymethylenepyridines, quinoline, isoquinoline and their

derivatives

Heterocyclic compounds : Six-membered heterocyclic compounds with a single nitro-gen atom in the ring; pyridine, polymethylenepyridines, quinoline, isoquinoline an d

their derivative s

PREFACE VII

OFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS XI V

LIST OF ABBREVIATED NAMES OF CHEMICAL FIRMS MENTIONED IN PATENT REF -ERENCES X V

LIST OF COMMON ABBREVIATIONS AND SYMBOLS USED XV I

Chapter 23 . Compounds containing a Six-Membered Ring withOne Hetero Atom, Nitrogen ; Introduction, Theoretical

Description and Spectroscopic Propertiesby MICHAEL H . PALME R

1. Introduction 12. Theoretical description 2

a . Molecular structures

2

(i) Molecular vibrations, 4 - (ii) Thermochemical studies, 5 - (iii) Magneti csusceptibility, 5 -

3. Spectroscopic properties 6a. Nuclear magnetic resonance

6(i) Proton magnetic resonance, 6 (ii) Carbon ( 13 C) magnetic resonance, 11 -(iii) Nitrogen magnetic resonance, 13 - (iv) Fluorine chemical shifts, 14 -(v) Effects of protonation on IH and 13 C chemical shifts and coupling con-stants, 15 -

b. Chemical shifts and electron density

1 5

(i) Lanthanide induced n .m .r . shifts (l .i .s .), 17 - (ii) Molecular electron distri-bution, 18 -

c. Ionisation processes 20d. Electron impact phenomena 22e. Radical anions 2 3

(i) Polarographic reduction, 23 - (ii) Solvated electrons from alkali metal solu -tions, 23 -

f. Excited electronic states 24

Chapter 24 . Compounds containing Six-Membered Ringswith one Nitrogen atom ; Pyridine and its Derivatives

by D . M . SMIT H

I . Introduction 2 7a. Historical 2 7b. Pyridine derivatives from coal tar and from petroleum 28c. The pyridine molecule 2 8d. Spectroscopic properties of pyridines 29

2 . Synthesis of pyridines 3 0a . From acyclic compounds

3 0

(i) Using ammonia or amines as sources of the ring nitrogen, 31 - (ii) Using a

cyano-group as the source of the ring nitrogen, 38 - (iii) Cyclisations no tinvolving C-N bond formation, 42 -

b. From other heterocyclic compounds

4 3(0 From 5-membered heterocyclic ring systems, 43 - (ii) From 6-membere dring systems, 48 - (iii) From other ring systems, 52 -

c. From carbocyclic compounds 5 3d. Separation and purification of pyridine bases 5 5

3 . Reaction of pyridines 5 6a. Pyridines as tertiary amines

5 6(i) Pyridinium salts, 56 - (ii) Pyridine-N-oxides, 60 - (iii) Pyridinium ylide sand related zwitterions, 67 -

b. Pyridines as benzene analogues : substitution at the ring carbon atoms

79(i) Electrophilic substitution, 79 -(ii) Nucleophilic substitution, 91 - (iii) Typica lnucleophilic substitutions, 96 - (iv) Order of substituent mobility in nucleo-philic substitution, 128 - (v) Radical substitution, 130 - (vi) Photochemica lreactions of pyridine and its derivatives, 135 - (vii) Non-photochemical rin gfission, ring expansion and contraction and rearrangement, 145 -

4 . Individual compounds 15 1a . Pyridines and their derivatives

15 1

(i) Pyridine, 151 - (ii) Pyridine homologues ; alkylpyridines, 152 - (iii) Alkenyl-pyridines, 159 -(iv) Benzylpyridines, 160 - (v) Arylpyridines, 160 - (vi) Pyridon emethides, 161 - (vii) Halogenopyridines, 162 - (viii) Nitropyridines, 166 - (ix)Pyridinesulphonic acids and pyridinesulphonyl compounds, 167 - (x) Reductio nproducts of nitropyridines, 168 - (xi) Hydroxypyridines and pyridones, 174 -(xii) Pyridinethiols, pyridinethiones (thiopyridones), and their derivatives, 178 -(xiii) Pyridyl alcohols, 180 - (xiv) Pyridinecarbaldehydes, 181 - (xv) Pyridy lketones, 183 - (xvi) Pyridinecarboxylic acids, 185 - (xvii) Cyanopyridines, 189 -(xviii) Pyridine derivatives containing phosphorus and arsenic, 190 -

5 . Bi-, ter- and quater-pyridyls 19 16 . Dehydropyridines 19 4

a . o-Dehydropyridines (pyridynes)

19 4

(i) Formation, 194 -(ii) Reactions of pyridynes with arynophiles and dipolaro-philes, 197 - (iii) Nucleophilic addition to pyridynes, 200 - (iv) Pyridyne-N -oxides, 201 - (v) Other dehydropyridines, 203 -

7 . Hydrogenated pyridine derivatives 20 4a. Dihydropyridines

20 4(i) Preparation, 204 - (ii) Properties, 206 -

b. Tetrahydropyridines (piperideines)

20 7(i) Preparation, 208 - (iii) Properties, 211 -

c. Hexahydropyridines (piperidines)

21 2(i) Preparation, 212 - (ii) Stereochemistry, 212 - (iii) Piperidine and its C- an dN-alkyl- and -aryl-derivatives, 213 - (iv) Fission of the piperidine ring, 216 - -(v) Aminopiperidines and hydroxypiperidines, 218 - (vi) Piperidinecarboxyli cacids, 220 - (vii) Piperidones, 222 -

8 . Bipiperidyls 224

Chapter 25 . Bicyclic compounds containing a Pyridine Ring :Cyclopolymethylenepyridines, Cycloalkenopyridine s

by N . CAMPBELL 22 7

Chapter 26. Bicyclic compounds containing a Pyridin eRing: Quinoline and its Derivative s

by N. CAMPBEL L

1 . Introduction 23 1a . Occurrence and structure of quinoline

23 1

(i) Occurrence, 231 - (ii) The structure of quinoline, 232 - (iii) The fine structureof quinoline, 233 -

2_ Methods of synthesis 23 4a. The Friedländer and Pfitzinger syntheses

23 5

(i) The Friedländer synthesis, 235 - (ii) Pfitzinger synthesis, 236 -

b. Skraup syntheses and related methods

23 6(i) The Skraup synthesis, 236 - (ii) The Döbner-von Miller synthesis, 238 -(iii) Döbner's cinchoninic acid synthesis, 239 - (iv) Conrad-Limpach and Knor rsyntheses, 240 - (v) Combes synthesis, 241 - (vi) The Gagan-Lloyd method ,242 -

c. Syntheses from 2-nitrobenzylidene derivatives 242d. Miscellaneous syntheses

24 3(i) From bicyclic compounds, 243 - (ii) From N-phenylmaleimide, 244 - (iii)From acetylenedicarboxylic esters, 244 -

e. Separation, purification and identification of the quinoline bases 2443 . Properties of the quinoline bases 246

a. Physical properties 246b. Chemical properties ; reactions

24 7(i) Oxidation, 247 - (ii) Reduction, 248 - (iii) N-Acylation ; formation and reac-tions of N-acylquinolium salts, 248 - (iv) Quinoline as an aromatic compound ,249-(v) Substitution, 250-(vi) Addition at the azomethine (1,2) linkage, 257 -(vii) Quinoline as a cyclic azomethine, 259 - (viii) Quinolynes, 261 - (ix) Quin-olinium compounds, 262 - (x) Quinoline N-oxides, 266 - (xi) Pseudo-bases ,271 - (xir) Ring-fission, 274 -

c. Skeletal changes in the quinoline series

27 5(i) Ring-expansion, 276 - (ii) Ring-contraction, 279 -

4 . Quinoline, its homologues and substituted compounds 28 1a. Quinoline and related bases

28 1(i) Quinoline, 281 - (ii) Quinoline homologues, 282 - (iii) Di-2-quinolylmethaneand related compounds, 284 - (iv) Phenylquinolines, 286 - (v) Quinolonemethides, 288 -

b. Substituted quinolines

290(i) Halogenoquinolines, 290 - (ii) Nitroquinolines, 294 - (iii) Quinoline-sulphonic acids, 298 - (iv) Aminoquinolines, 299 - (v) Hydrazinoquinoline sand related compounds, 308 - (vi) Quinolinols or hydroxyquinolines : quin-olones, 309 - (vii) Aminoquinolinols and aminoquinolones, 325 - (viii) Quino-linequinones, 327 - (ix) Quinolinethiols, 328 - (x) Quinolinecarbaldehydes,

330 - (xi) Quinolyl ketones, 334 - (xii) Quinolinecarboxylic acids, 334 -(xiii) Hydroxyquinolinecarboxylic acids, 340 - (xiv) Quinophthalones : quin-oline dyes, 343 -

5, Biquinolines 3446 . Hydrogenated quinolines 346

a. Dihydroquinolines

346

(i) 1,2-Dihydroquinolines, 346 -- (ii) 1,4-Dihydroquinoline, 349 - (iii) 5,6- an d5,8-Dihydroquinolines, 350 -

b. Tetrahydroquinolines 35 1c. I lexahydroquinolines 35 5d. Decahydroquinolines 35 5

Chapter 27 . Bicyclic compounds containing a PyridineRing ; Isoquinoline and its Derivatives

by S . F . DYK E

1 . Introduction 35 7a. The synthesis of isoquinolines 35 8

(i) Type 1 syntheses, 359 - (ii) Type 2 syntheses, 376 - (iii) Type 3 syntheses,381 - (iv) Types 4 and 5 syntheses, 383-(v) Summary of synthetic methods, 387 -

b. Physical properties of the isoquinolines 38 8

(1) Physical constants, 388 - (ii) Spectral properties, 394 -

c. The chemical properties of isoquinolines

39 9

(i) Reduction, 399 - (ii) Oxidation, 401 - (iii) Substitution reactions, 403 -(iv) Pseudobases and pseudosalts, 406 - (v) Ring-opening reactions, 410 -(vi) Reactions involving substituents, 413 - (vii) Hydroxyisoquinolines andtautomerism, 416 - (viii) Rearrangement reactions, 419 - (ix) Isocarbostyrils ,421 - (x) Reissert compounds, 424 - (xi) Isoquinolinecarbaldehydes and iso-quinolyl ketones, 426 - (xii) Isoquinolinccarboxylic acids, 426 -

2 . Hydroisoquinolines 427a. Py-Hydroisoquinolines

427

(i) 3,4-Dihydroisoquinolines, 427 - (ii) 1,2-Dihydroisoquinolines, 428 -

b. Ar-Hydroisoquinolines 43 03 . Biisoquinolyls 433

a. 1,1'-Biisoquinolyl derivatives 434b. 1,2'-Biisoquinolyl derivatives 43 6c. 2,2'-Biisoquinolyls 436d. 4,4'-Biisoquinolyl derivatives 437e. 3,4'-Biisoquinolyls 437f. 8,8'-Biisoquinolyl derivatives 438

Index 439