RODD'S CHEMISTRY

OF CARBON COMPOUND S

A modern comprehensive treatise

SECOND EDITION

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 B

HETEROCYCLIC COMPOUND S

Five-membered heterocyclic compounds with a single hetero-atom in th ering : alkaloids, dyes and pigments

Heterocyclic Compounds : Five-membered heterocyclic compounds with a singl ehetero-atom in the ring : alkaloids, dyes and pigments

PREFACE VI I

OFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS XVLIST OF ABBREVIATED NAMES OF CHEMICAL FIRMS MENTIONED IN PATENT REFER-

ENCES XV ILIST OF COMMON ABBREVIATIONS AND SYMBOLS USED XVI I

Chapter 7. Five-Membered Monoheterocycli cCompounds (continued) : Pyrrolidine Alkaloids

by J . D . HUNT AND A. MCKILLOP I

Chapter 8 . Five-Membered Monoheterocycli cCompounds Alkaloids (continued) :

Pyrrolizidine Alkaloidsby H. C . S . WOOD AND R . WRIGGLES WORT H

1 . Necines 8a. Unhydroxylated derivatives 9b. Monohydroxylated derivatives

1 0

(i) 7-Hydroxy-l-methylenepyrrolizidines, 10 - (ii) 1-Hydroxymethylpyrrolizi-dines, 10 -

c. Dihydroxylated derivatives

1 3(i) 1-Hydroxymethyl-7-hydroxypyrrolizidines, 13 - (ii) Dehydro-7-hydroxy-l-hydroxymethylpyrrolizidines, 15 - (iii) 2-Hydroxy-l-hydroxymethylpyrrolizi-dine, 17 -

d. Trihydroxylated derivatives 1 72 . Necic acids 1 9

a. C 4 -Acid 20b. C 5 -Acids 20c. C 6 -Acids 2 1d. C,-Acids and derivatives 2 1e. C 8 -Acids 24f. C 1 o-Glutaric acids 2 6g. C 10 -Adipic acids

29

(z) Senecic acid, 29 - (ii) Sceleranecic acid (dilactone), 35 -3 . Alkaloids 3 7

a. Rates of hydrolysis 3 7b. Hydrogenolysis 3 7

4 . Miscellaneous types of pyrrolizidine alkaloids 5 9a . Loline group alkaloids 60

5 . Pharmacology of the pyrrolizidine alkaloids 61

Chapter 9 . The Indole Alkaloidsby K. S . J . STAPLEFORD

1 . Alkaloids lacking a tryptamine unit 65a. Simple indoles 65b. Carbazole derivatives 66

2 . Alkaloids containing a tryptamine unit 70a. Compounds without an isoprene moiety

7 1(i) Simple tryptamines, 71 - (ii) Alkaloids of the Calabar bean, 72 - (iii) ß-Car-boline and reduced ß-carbolines, 75 -

b. Compounds containing an isoprene (but not terpene) derived moiety . .

76(r) The ergot alkaloids, 76 - (ir) The brevianamides, echinulin and relate dcompounds, 79 -

c. Compounds containing a terpene-derived moiety

8 5(i) Alkaloids with the Corynanthe-Strychnos unit, 88 - (ii) Alkaloids with aseco-type unit, 118 - (iii) Alkaloids with the Aspidosperma unit, 119 - (iv)Alkaloids containing the Iboga unit, 138-(v) Novel types, 144-

3 . Bisindole alkaloids 146a. Compounds containing two identical "halves" linked symmetrically

147(i) Calycanthaceous alkaloids, 147- (ii) Calabash-curare alkaloids, 149-

b. Compounds not composed of identical halves nor linked symmetrically

15 1(i) The Roxburghines and sesquimeric compounds, 151 - (ii) The secamines an dpresecamines, 152 - (iii) Bisindoles from Vinca rosea, 157 - (iv) Other repre-sentative bisindole alkaloids, 159 -

Chapter 10 . Five-membered Monoheterocycli cCompounds . Alkaloids (continued) :

Amaryllidaceae Alkaloidsby M . SAINSBUR Y

1. Introduction 16 5a . Structural types 16 5

2. Biosynthesis 17 93. The individual alkaloids 18 4

a. Pyrrolo[1,2,3-d,e]phenanthridine alkaloids 18 4b. 2-Benzopyrano[3,4-g]indole alkaloids 18 8c. Galanthamine-type alkaloids 190d. [5,10b]-Ethanophenanthridine alkaloids 192e. Pretazettine-type alkaloids 19 5f. Montanine, coccinine and manthine (5, 1 1-Methanom orphanthrine types) 19 6g. Miscellaneous alkaloids 19 7

Chapter 11 . Five-membered Monoheterocycli cCompounds : Alkaloids (continued) :

Tropane Alkaloidsby H. C . S . WOOD and R . WRIGGLESWORT H

1 . Introduction 201

a. General synthetic methods

20 2

(i) Robinson-Schöpf synthesis, 202 - (ii) From pyrrolidines, 203 - (iii) From2,6-cycloheptadienone, 204 - (iv) From cyclopropanones and pyrroles, 204 -

b. Stereochemical aspects 20 52 . The tropane alkaloids 209

a. Monohydroxytropanes

21 0

(i) Dipole moment data, 212 - (ii) Infra-red data, 212 - (iii) X-Ray data ,212 - (iv) Acyl migration data, 212 -

b. Dihydroxytropanes 21 8c. Trihydroxytropane derivatives 222d. Cocaines and ecgonines 228e. Miscellaneous tropane alkaloids 232f. Pharmacological and metabolic properties of tropane alkaloids 23 3

3 . N-Methylgranatanine alkaloids 23 3

Chapter 12 . Five-membered Monoheterocyclic Compounds (continued) :The Pyrrole Pigments

by K.M . SMIT H

1 . Open-chain pigments 239a. Pyrromethenes

23 9

(i) Methods of synthesis, 239 - (ii) Properties and reactions, 240 -

b. Bile pigments

24 4

(i) Synthetic methods, 246 - (ii) Individual compounds, 249 - (iii) Bile pigment sin plants, 252 - (iv) Diagnostic reactions, 252 -

2 . Macrocyclic pigments : unreduced porphyrins 25 3a. Synthetic methods

25 4

(i) By polymerisation of monopyrroles, 254 - (ii) From dipyrrolic compounds ,

256 - (iii) From open-chain tetrapyrroles, 263 -

b. General properties

26 7

(i) Metal-free porphyrins, 267 - (ii) Metalloporphyrins, 271 -

c. Porphin and its simple derivatives 27 3d. Porphyrinpropionic acids 27 7e. Haemoglobin

27 7

(I) Structure of protoporphyrin-IX, 278 - (ii) Haemoglobin : properties andtransformations, 280 -

f. Other porphyrin-protein complexes 28 1g. Naturally occurring protein-free porphyrins 28 3

3 . Reduced porphyrins . Chlorophyll 28 5a. Synthetic reduced porphyrins

28 6

(i) Dihydroporphyrins, 286 - (it) More highly reduced porphyrins, 288 -

b. Chlorophylls

28 9

(I) Chlorophyll-a, 291 - (ii) Chlorophyll-b, 298 - (iii) Bacteriochlorophyll ,299 -

c. Vitamin B 12 (cyanocobalamin)

300

(i) Simple corrins, 303 - (ii) Vitamin B, 2 , 305 -

4 . Structural analogues of porphyrins 30 6a. Corroles

30 6(i) Synthetic aspects, 306 - (ii) Reactions, 307 -

b. Tetrahydrocorrins

30 8(i) Synthetic aspects, 308 - (ii) Reactions and properties, 309 -

c. Sapphyrins 31 1d. Porphyrin analogues containing other hetero-atoms 31 2

5 . Biosynthesis of pyrrole pigments 31 3a. Open-chain pigments

31 3(i) Prodigiosin, 313 - (ii) Bile pigments, 314 -

b. Haem 31 6c. Chlorophylls 32 1d. Vitamin B,, 322

6 . Applications of spectroscopic techniques 32 3a. Electronic absorption spectroscopy 32 3b. Nuclear magnetic resonance spectroscopy 32 4c. Electron paramagnetic resooance spectroscopy 32 5d. Mass spectrometry 32 6e. X-ray studies 32 6

Chapter 13 . Five-Membered Monoheterocycli cCompounds (continued) : Azaporphins ;

Benzopolphins ; Phthalocyanines an dRelated Structures

by V . D . POOL E1 . Azaporphins 33 0

a. Monoazaporphins 33 0b. Diazaporphins 33 0c. Tetra-azaporphins 33 1

2 . Benzoporphins 33 23 . Benzo-mono-, -di-, and -tri-azaporphins 33 34 . Tetrabenzotetra-azaporphins(phthalocyanines) 33 45 . Macrocycles related to phthalocyanine 33 9

Chapter 14 . Five-Membered MonoheterocyclicCompounds (continued) : The Indigo Group

by M . SAINSBUR Y

I . Indigo (Indigotin) and its derivatives 34 2a. Indigo (indigotin)

342(i) Constitution, 343 - (ii) Synthetic methods, 345 - (iii) Properties and reac-tions of indigotin, 348 -

b. Derivatives of indigotin

350(i) N-Derivatives of indigotin, 350 - (ii) Derivatives of the carbonyl function ,351 - (iii) Homologues of indigotin, 352 - (iv) Halogenoindigos, 352 - (v) Othersubstituted indigos, 353 - (vi) Dehydroindigo, 354 - (vii) Leuco-indigo (indigo -white), 354 - (viii) Polycyclic indigos, 355 -

2. Indirubin 35 63. Isoindigo 358

4. Other indigoid pigments 35 9a. Thioindigos 35 9b. Indigoid derivatives containing nitrogen and sulphur 36 5c. Selenoindigo 36 7d. Vinylene homologues of the indigos 36 7

Chapter 15. Five-Membered Monoheterocyclic Compounds(continued) : Cyanine Dyes and Related Compounds

by D . J . FR Y

1 . Cyanines 37 0a. Methods of preparation

37 3(i) Monomcthinecyanines, 373 - (ii) Trimethinecyanines, 375 - (iii) Mesa-sub-

stituted unsymmetrical trimethinecyanines, 378 - (iv) Trimethinecyanines withmiscellaneous substituents, 379 - (v) Penta- and higher poly-methinecyanines,381 - (vi) Dyes derived from uncommon nitrogen heterocycles, 384 - (vii)Dyes from non-nitrogenous heterocycles, 385 - (viii) Substituents on the nitro -gen atoms, 387 -

b. Properties of the cyanine dyes 38 8c. Typical compounds 39 3

2 . Aza-, phospha-, and arsa-cyanines 39 5a. Azamonomethinecyanines 39 5b. Azatrimethinecyanines 39 6c. Azapentamethinecyanines 39 7d. Phospha- and arsa-cyanines 39 8

3 . Polynuclear cyanines 39 84 . Dye bases 40 15 . Merocyanines 40 2

a. Methods of preparation 402b. Properties of the merocyanine dyes 40 5c. Typical compounds 40 7

6 . Linear tri- and poly-nuclear cyanines and merocyanines 40 77 . Oxonol dyes 41 08 . Non-heterocyclic cyanines 41 1

a. Streptocyanines 41 1b. Cyanines with carbocyclic terminal groups 41 5

9 . Styryl dyes and hemicyanines 41 6,a . Styryl dyes 41 6b . Azastyryl dyes 41 7c . Hemicyanines 41 8

10. Reaction mechanisms 42 0

Index 423