RODD'S CHEMISTR Y

OF CARBON COMPOUND S

A modern comprehensive treatis e

SECOND EDITIO N

Edited by

S . COFFE Y

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

I.C.I. Dyestuffs Division, Blackley, Mancheste r

VOLUME IV PART G

HETEROCYCLIC COMPOUND S

Six-membered heterocyclic compounds with a single nitrogen atom in thering to which are fused two or more carbocyclic ring systems, and six-membered ring compounds where the hetero-atom is phosphorus, arsenic ,antimony or bismuth . Alkaloids containing a six-membered heterocycli c

ring system

Heterocyclic Compounds : Six-membered heterocyclic compounds with a single nitro -gen atom in the ring to which are fused two or more carbocyclic ring systems, an dsix-membered ring compounds where the hetero-atom is phosphorus, arsenic, anti-mony or bismuth . Alkaloids containing a six-membered heterocyclic ring system .

PREFACE VII

OFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS XIV

LIST OF COMMON ABBREVIATIONS AND SYMBOLS USED XV I

Chapter 28 . Poly cyclic Compounds Comprising a Pyridine and Two or MoreCarbocyclic Rings

by N . CAMPBEL L

1 . Acridine and its derivatives 1a. General introduction to the chemistry of acridine

1

(i) Methods of preparation, 4 - (ii) Physical properties, 7 - (iii) Chemical prop-erties and reactions, 8 -

b. Acridine and substituted acridines

1 5

(i) Acridine and homologues, 15 - (ii) Halogenoacridines, 18 - (iii) Nitro-acridines, 19 - (iv) Aminoacridines, 19 - (v) Hydroxyacridines, 23 -

c. 9,9'-Biacridines and related compounds 2 5d. Hydrogenated acridines and their derivatives

2 8

(i) Hydroacridines, 28 - (ii) 9-Acridone (acridanone), 31 - (iii) 9-Acridone-quinones, 35 - (iv) Thioacridone, 35 -

e. Acridine dyes

3 6

(i) Basic dyestuffs, 36 - (ii) Vat dyestuffs, 37 - (iii) Pigments . Quinacridines ,quinacridones, 38 -

2 . Phenanthridine and its derivatives 40a. Methods of synthesis 4 1b. Phenanthridines

43

(i) General physical properties, 43 - (ii) Chemical properties, 44 -

c. Substituted phenanthridines

49

(i) Alkylphenanthridines, 49 - (ii) Halogenophenanthridines, 51 - (iii) Nitro -and amino-phenanthridines, 52 - (iv) Hydroxyphenanthridines or phenanthrid-inols, 53 - (v) Phenanthridones, 53 -

d. Hydrogenated phenanthridines 5 7

3 . Benzo[f ], [g] and [h]quinolines 60a. Structure and synthesis 60b. Properties 62

4 . Benzisoquinolines 66a. Benz[f]isoquinolines 66b. Benz[g]isoquinoline 68

5 . Naphthoquinolines and naphthoisoquinolines 7 16 . Benzacridines and benzophenanthridines 7 5

a. Benzacridines 7 5b. Benzophenanthridines 78

Chapter 29 . Six-membered Heterocycles Containing Phosphorus, Arsenic ,Antimony and Bismuth as a Single Heteroatom

by R . E . ATKINSO N

1 . Phosphorus compounds 8 3a. Phosphorinane and its derivatives 8 3

(i) Phosphorinanes, 83 - (ii) Phosphorinanones, 86 - (iii) Phosphorinanols, 88 -b. Tetrahydrophosphorins and related compounds 89

(i) Tetrahydrosphosphorins, 89 - (ii) Tetrahydrophosphinolines, 91 -

c. Dihydrophosphorins 93d. Phosphorins, phosphabenzenes 97e. Miscellaneous phosphorus heterocycles

104

(i) Heterocycles containing bridgehead phosphorus, 104 - (ii) 5-Phospho-niaspiro[4.5]decane derivatives, 105 -

2 . Arsenic compounds 105Arsenanes and related compounds

105

(i) Arsenanes, 105 - (ii) 4-Arsenones, 106- (iii) Derivatives of tetrahydroarsenin ,tetrahydroarsinoline and tetrahydroisoarsinoline, 108 -(iv) 5,10-Dihydroacrid-arsines and 5,6-dihydroarsanthridincs, 110 - (v) 1 H-Naphth[1,8-c,d]arsenins ,112 - (vi) Arsenins, 112 -

3 . Antimony compounds 11 34 . Bismuth compounds 11 4

Chapter 30. Pyridine and Piperidine Alkaloidsby J . D . HUNT AND A . MCKILLO P

a. Alkaloids of areca nut 11 9b. Alkaloids of hemlock 120c. Alkaloids of pomegranate root bark 12 6d. Lobelia and sedum alkaloids 12 8e. Alkaloids of tobacco 13 7f. Miscellaneous alkaloids 144

Chapter 31 . The Quinoline Alkaloidsby M . SAINSBUR Y

1 . Quinoline alkaloids of the Rutacea family 17 1a. Simple quinolines 19 3b. Simple quinolones 19 5c. Furoquinolines and furoquinolones 20 1d. Pyranoquinolines 20 9e. Acridone alkaloids 21 0f. Biosynthesis of the rutaceous quinoline alkaloids 21 4

2 . Miscellaneous alkaloids of probable biogenetic derivation from anthranilicacid 21 6a. Echinorine and echinine 21 6b. The alkaloids of Macrorungia longistrobus 21 7c. Cryptolepine 220

3. Miscellaneous alkaloids containing the quinoline ring system 22 0a . Quinolines from fungi and micro-organisms

22 1

(i) Pseudanes, 221 - (ii) Viridicatine, viridicatol, cyclopenine and cyclopenol ,222 -

4. Quinoline alkaloids derived from tryptophan 22 5a. The cinchona alkaloids

225

(i) Occurrence, 225 - (ii) Individual quinoline alkaloids and related compounds,226 - (iii) Cinchona alkaloids derived from indole, 232 - (iv) Stereochemistryof the cinchona bases, 234 - (v) Physical properties of cinchona bases, 239 -(vi) Synthetical studies in the cinchona series, 239-(vii) Biosynthesis of cinchon aalkaloids, 244 -

b. Camptothecin 24 6c. Calycanthine, calycanthidine, folicanthine, chimonanthine and meso-

chimonanthine 24 9

(i) Calycanthine, 249 - (ii) Folicanthine and chimonanthine, 250 - (iii) calycan-thidine, 250 - (iv) Biosynthesis of the calycanthaceous alkaloids, 251 -

d. 2-Quinolone alkaloids of Melodinus scandens

252

(i) Meloscine and epimeloscine, 252 - (ii) Scandine and meloscandonine, 252 -(iii) Perloline and perlolidine, 253 - (iv) Perhydroquinolines, 254 -

Chapter 32 . The Acridine Alkaloidsby B . P . S WANN AND A . MCKILLO P

Spectral characteristics 25 8Reactions of acridone alkaloids 25 9The acronycine group of alkaloids 26 3

Chapter 33 . The Alkaloids of the Morphine Groupby K . W . BENTLE Y

1 . The morphine-thebaine group 26 8a. Structure 270b. Total synthesis of morphine 275c. Stereochemistry

27 8

(i) Morphine alkaloids, 278 - (ii) B/C-trans-morphine and its derivatives, 281 -

d. Reactions and derivatives of the morphine-thebaine group of alkaloids 28 3

(i) The halogeno-morphides and -codides, 283 - (ii) Exhaustive methylation o fcodeine, 284 - (iii) The deoxy compounds, 285 - (iv) The reduction of thebaine,286 - (v) The thebainones, 288 - (vi) The thiocodides, 290 - (vii) 14-Bromo- and14-hydroxy-codeinone, 290-(viii) Migration of nitrogen from C-9 to C-I4, 291 -(ix) Diels-Alder reactions of thebaine, 292 - (x) Molecular rearrangement sinvolving the C-13 side-chain, 294 - (xi) Molecular rearrangements not involv-ing the C-13 side-chain, 297 - (xii) Flavothebaone, 299 - (xiii) Reaction o fthebaine with metal carbonyls, 300 - (xiv) 0-Morphine, 301 -

e. The relationship between structure and analgesic activity 30 12 . The sinomenine-salutaridine group 30 23 . The hasubanonine group 30 94 . The homomorphine alkaloids 319

Chapter 34 . Diterpenoid Alkaloidsby A . R . PINDE R

1 . C20 -diterpene alkaloids 32 4a. The Garrya alkaloids 32 4b. The atisine alkaloids 33 4c. Alkaloids with a modified atisane skeleton 34 1

2 . C19 -diterpene alkaloids 350a. Lycoctonine-type alkaloids 35 0b. Aconitine-type alkaloids 35 8c. Lactonic alkaloids 37 0d. Daphniphyllum alkaloids

37 4

(i) Daphniphylline subgroup, 374 - (ii) Secodaphniphylline subgroup, 376 -(iii) Yuzurimine subgroup, 376 -

3 . Bis-diterpene alkaloids 37 8

Chapter 35 . Steroidal Alkaloidsby A. R . PINDE R

1 . Normal steroidal alkaloids 38 1a. Bases related to 3-amino-5a-pregnane 382b. Bases related to 20-amino-5a-pregnane 38 9c. Bases related to 3,20-diamino-5a-pregnane 39 1d. Bases related to 3-aminoconanine 39 9e. Bases related to 20-piperidyl-5a-pregnane

41 1(i) Simple bases, 411 - (ii) Solanidanes, 415 - (iii) Spirosolane alkaloids, 422 -

f. Biosynthesis of normal steroidal alkaloids 42 6g. Biological properties of normal steroidal alkaloids 42 7

2 . Alkaloids with a modified steroidal structure 42 7a. Salamander alkaloids

430

(i) Alkaloids containing an oxazolidine ring, 431 - (ii) Alkaloids not containin gan oxazolidine ring, 434 - (iii) Biosynthesis of salamander bases, 435 - (iv )Physiological action, 435 -

b. C-Nor-D-homosteroidal alkaloids 43 6

(i) Alkamines, 437 - (ii) Ester-alkaloids, 444 - (iii) Fritillaria alkaloids, 453 -

e. Buxus alkaloids 45 4

(i) Monoacidic Buxus alkaloids, 455 - (ii) Diacidic Buxus alkaloids, 459 -

INDEX 467