n

Supplements to the 2nd Edition (Editor S. Coffey) of

RODD'S CHEMISTRY OF

CARBON COMPOUND S

A modern comprehensive treatis e

Edited byMARTIN F . ANSELL

Ph.D., D.Sc . (London) F.R.S.C. C. Chem.Reader Emeritus, Department of Chemistry ,

Queen Mary College, University of London, Great Britai n

Supplement to

VOLUME IV HETEROCYCLIC COMPOUND S

Part H :Six-Membered Heterocyclic Compounds with (a) a Nitrogen Atom Commonto Two or More Fused Rings ; (b) One Hetero-atom in Each of Two FusedRings. Six-Membered Ring Compounds with Two Hetero-atoms fromGroups VI B, or V B and VI B of the Periodic Table, respectively .

Isoquinoline, Lupinane and Quinolizidine Alkaloids

Heterocyclic Compounds : Six-Membered Heterocyclic Compounds with (a) a Nitrogen Ato mCommon to Two or More Fused Rings ; (b) One Hetero-atom in Each of Two Fused Rings . Six-Membered Ring Compounds, with Two Hetero-atoms from Groups VI B, or V B and VI B ofthe Periodic Table, respectively . Isoquinoline, Lupinane and Quinolizidine alkaloid s

Preface : :: :iäi :i .:e~ : +► s~:i burr{r: 7r ,.::;s::. ..

VIIOfficial publications ; scientific journals and periodicals XII IList of common abbreviations and symbols used XIV

Chapter 36. Alkaloids of the Morphine-Hasubanonine Groupby K.W. BENTLEY

1. New morphine alkaloids 12. O- and N-deniethylations 43. Codeine and its reactions üä::ß:ä::„„ ;s„, ;;:,li:, ; ; 54. Dihydrocodeinone and its reactions 75. 14-Substituted codeinones 1 26. Thebaine and its analogues 1 47. Alkaloids of the sinomenine-salutaridine group 1 88. Hasubanan alkaloids 209. Homomorphine alkaloids 20

10. Syntheses in the morphine-hasubanan group 22

Chapter 37. Fused Heterocyclic Systems having a Nitrogen Atom Common toTwo orMore Rings

by D . LEAVE R

1 . Indolizines 3 3(a) Aromatic indolizines 3 3(b) Indolizidines and partially reduced indolizines 3 6

2 . Quinolizines 3 9(a) Aromatic quinolizines 3 9(b) Quinolizidines and partially reduced quinolizines 4 2

3 . Azepine derivatives containing a bridgehead nitrogen atom 4 24 . Tricyclic compounds with nitrogen common to all three rings 4 5

(a) [2 .2 .3]Cyclazines (pyrrolo[2,1, 5-cd]indolizines) 4 5(b) [2 .3 .3]Cyclazines (pyrrolo[2,1,5-de]quinolizines) and

[2 .2 .4]cyclazines (azepino[2,1,7-cd]pyrrolizines) 4 6(c) [3 .3 .3]Cyclazines (pyrido[2,1,6-de]quinolizines) and

[2 .3 .4]cyclazines (azepino[2,1,7-cd]indolizines) 4 $5 . Bridged ring compounds 5 2

(a) Bicyclic systems having a nitrogen bridge 5 2(b) Bicyclic systems having nitrogen at a bridgehead position 53

Chapter 38 . The Quinolizine Alkaloidsby M. SAINSBURY

Introduction 5 51 . Lupinine alkaloids and related compounds 5 7

(a) New structures 5 7(b) Syntheses 6 2

2 . Alkaloids of the cytisine type 6 73 . Lupanine alkaloids 7 04. Quinolizidine - indolizidine alkaloids 7 25 . Ormosia alkaloids 7 36 . Matrine-like alkaloids and their congeners 7 57 . 9b-Azaphenalene alkaloids 7 9

(a) The bases 7 9(b) Syntheses 8 1

Chapter 39. Compounds Containing Two Fused Five- and Six-MemberedHeterocyclic Rings each with One Hetero-ato m

by D .T . HURST

1 . Compounds containing two hetero rings fused to an aromatic system 8 7(a) Furoquinolines 8 7(b) Pyrroloquinolines 8 8(c) Phenanthrolines 8 8

2 . Compounds containing two hetero rings fused through adjacent carbo natoms 9 0(a) Furopyrroles 9 0(b) Furopyridines 9 0(c) Furoquinolines 9 5(d) Pyranopyridines 9 8(e) Benzopyranopyridines 10 0(f) Pyrrolopyridines or azaindoles 10 2

(g) Carbolines (pyridinoles) 10 9(h) Naphthyridines (diazanaphthalencs) 11 3(i) Benzonaphthyridines (diaza-anthracenes and -phenanthrenes) an d

related compounds 12 3

(j) Other ring systems 12 9

Chapter 40. Compounds Containing a Six-Membered Ring having Two Hetero-atoms from Group VIB of the Periodic Table: Dioxanes, Oxathianes an d

Dithianesby M . SAINSBURY

1 . Dioxanes and related compounds 13 1(a) 1,2-Dioxanes, 1,2-dioxins and related compounds

13 1(i) 1,2-Dioxanes, 131 - (ii) 1,2-Dioxins (1,2-dioxenes), 132 -

(b) 1,3-Dioxanes, 1,3-dioxins and allied compounds

13 5(i) 1,3-Dioxanes, 135-(ii) 1,3-Dioxins and 1,3-dioxinones, 144-(iii )Benzo-l,3-dioxins, 146-

(c) 1,4-Dioxanes, 1,4-dioxins and 2,3-dihydro-1,4-dioxins

148(i) 1,4-Dioxanes, 148 - (ii) 1,4-Dioxins and 2,3-dihydro-1,4-dioxins,151 - (iii) 1,4-Benzodioxin and its derivatives, 155 -

2 . Dithianes, dithiins and their benzo derivatives 15 7(a) 1,2-Dithiins and benzo-1,2-dithiins 15 7(b) 1,3-Dithianes and 1,3-dithiins

15 9(i) 1,3-Dithianes, 159 - (ii) 1,3-Dithiins, 166 -

(c) 1,4-Dithiins, 2,3-dihydro-1,4-dithiin, 1,4-dithianes and their benz oderivatives 16 6(i) 1,4-Dithiins and their reduced forms, 166 - (ii) Benzodithiins, 16 9- (iii) Thianthrenes, 171 -

(d) Telluranthrenes 17 23 . Oxathianes, oxathiins and related compounds 17 3

(a) 1,2-Oxathianes, 1,2-oxathiins and their benzo derivatives

17 3(i) 1,2-Oxathianes, 173 - (ii) 1,2-Oxathiins, 174 - (iii) 1,2 -Benzoxathianes and 1,2-benzoxathiins, 175 -

(b) 1,3-Oxathianes 17 7(c) 1,4-Oxathianes, 1,4-oxathiins and related structures

17 8(i) 1,4-Oxathianes, 178 - (ii) 1,4-Oxathiins, 179 - (iii) 1,4 -Benzoxathiins, 181 - (iv) Phenoxathiins and azaphenoxathiins, 182 -

Chapter 41 . Compounds Containing a Six-Membered Ring with Two Hetero -atoms from Groups Vand VI, respectively of the Periodic Table . Oxazines,

Thiazines and Their Analoguesby M . SAINSBURY

I . Oxazines 18 3(a) 1,2-Oxazines and their reduced forms

18 3(i) 2H-1,2-Oxazines, 183 - (ii) 6H-1,2-Oxazines, 185 - (iii) Dihydro-1,2-oxazines, 186 - (iv) Tetrahydro-1,2-oxazines, 191 -

(b) 1,3-Oxazines and their reduced forms

1~2(i) 2I1-1,3-Oxazines, 192 - (ii) 4H-1,3-Oxazines, 193 - (iii) 1,3-Oxazinium salts and mesoionic structures, 197 - (iv) Dihydro-l,3 -oxazines, 198- (v) Tetrahydro-1,3-oxazines, 204 -

(c) 1,4-Oxazines

;:206(i) Dihydro-1,4-oxazines, 206 - (ii) Tetrahydro-1,4-oxazine s(morpholines), 207 -

2. Benzoxazines 20 9(a) 1,2-Benzoxazines

20 9(i) 1H-2,1-Benzoxazines, 209 - (ii) 1 H-2, 3-Benzoxazines, 210 -

(b) 1,3-Benzoxazines and reduced forms

21 2(i) 2H-1,3-Benzoxazines, 212 - (ii) 1,3-Benzoxazin-2-ones and 4-ones ,213 - (iii) Dihydro-1,3-benzoxazines, 214 - (iv) Dihydrobenz-1,3 -oxazinones and thiones, 214 - (v) 1,3-Benzoxazindiones and relate dcompounds, 215 -

(c) 3,1-Benzoxazines and reduced forms

21 6(i) 4H-3,1-Benzoxazines, 216 - (ii) 3,1-Benzoxazin-4-ones, 216 - (iii )2,4-Dihydro-IH-3,1-benzoxazines and related compounds, 217 -

(d) 1,4-Benzoxazines and reduced forms ate,

218

3 . Phenoxazines 22 24 . Thiazines 22 5

(a) 1,2-Thiazines and reduced forms 22 5(b) 1,3-Thiazines and related compounds

22 8(i) 1,3-Thiazines, 228 - (ii) 1,3-Thiazinium salts, 230 - (iii) Dihydro -1,3-thiazines, 231 - (iv) Tetrahydro-1,3-thiazines, 234 -

(c) 1,4-Thiazines and reduced forms

23 5(i) 1,4-Thiazines and dihydro-l,4-thiazines, 235 - (ii) Tetrahydro-1,4 -thiazines and thiazinones, 238-

5 . Benzothiazines 23 9(a) 1,2-, 2,1- and 2,3-Benzothiazines and related structures 23 9(b) 1,3-Benzothiazines and reduced forms

244(i) 2H- and 4H-1,3-Benzothiazines, 244 -

(c) 3,1-Benzothiazines and related forms 24 5(d) 1,4-Benzothiazines

248(i) 4H-1,4-Benzothiazines, 248 - (ii) 2,3-Dihydro-4H-1,4-benzothiazines, 250 -

6 . Phenothiazines 25 17 . Phenotellurazines 25 4

Index 255