RODD'S CHEMISTR Y

OF CARBON COMPOUND S

A modern comprehensive treatise

SECOND EDITION

Edited by

S. C O FFEYM.Sc. (London), D .Sc . (Leyden), C .Chem., F.R.I .C .

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

VOLUME IV PART K

HETEROCYCLIC COMPOUNDS

Six-membered heterocyclic compounds with two or more hetero-atoms on eor more of which are from Groups II, III, IV, V or VII of the Periodi cTable . Heterocyclic compounds with seven or more atoms in the ring

Heterocyclic Compounds : Six-membered heterocyclic compounds with two or mor ehetero-atoms one or more of which are from Groups II, III, IV, V or VII of the Periodi c

Table . Heterocyclic compounds with seven or more atoms in the rin g

PREFACE VII

OFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS XVIII

LIST OF ABBREVIATED NAMES OF CHEMICAL FIRMS MENTIONED IN PATENT REFERENCES

XIX

LIST OF COMMON ABBREVIATIONS AND SYMBOLS USED X X

Chapter 48 . Compounds with Six-Membered Heterocyclic Rings possessing Two or Mor eUnusual Hetero Atoms

by R . S . EDMUNDSO N

1 . Mercury compounds 1

2. Boron compounds 1a. 1,4-Dihydro-1,4-diborins 1b. Perhydro-1,3,5-triborins (1,3,5-triborinanes) 2

3 . Compounds of silicon, germanium and tin 3a. Compounds with two hetero atoms 3

(i) 1,2,3,6-Tetrahydro-l,2-disilins (1,2-disilacyclohex-4-enes), 1,2-dihydro-l,2 -disilins (1,2-disilacyclohexadienes), their benzologues and germanium analogues ,4 - (ii) Perhydro-1,2-disilins and their germanium analogues (1,2-disilacyclo-hexanes) . 6 - (iii) Tetrahydro-l,3-disilins (1,3-disilacyclohexenes) and relate dcompounds, 8 - (iv) Perhydro-l,3-disilins (1,3-disilacyclohexanes) and relate dcompounds, 9 - (v) 1,4-dihydro-1,4-disilins (1,4-disilacyclohexa-2,5-dienes) .Germanium and tin analogues, 10 - (vi) Perhydro-l,4-disilins (1,4-disilacyclo-hexanes) . Germanium and tin analogues, 14 -

b. Perhydro-1,3,5-trisilins (1,3,5-trisilacyclohexanes) 1 5c. Perhydrotetrasilins (tetrasilacyclohexanes) 1 9

4 . Compounds containing arsenic and phosphorus 1 9a. Compounds with two hetero atoms 1 9

(i) Tetrahydro- and hexahydro(perhydro)-1,2-diphosphorins and -arsenins(1,2-diphosphorinanes and 1,2-diarsenanes), 19 - (ii) Di- and tetra-hydro-l,3 -diphosphorins and benzologues . Hexahydro-l,3-diphosphorins (1,3-diphosphor-inanes). Arsenic analogues, 20 - (iii) 1,4-Diphosphorins, 1,4-diarsenins and theirdi- and tetra-hydro derivatives. Perhydro-1,4-diphosphorins (1,4-diphosphor-inanes) and-1,4-diarsenins (1,4-diarsenanes), 22-(iv) Perhydro-l,4-diphosphorins(1,4-diphosphorinanes) and their arsenic analogues, 28 -

b. Compounds containing four hetero atoms

3 1

(i) 1,2,4,5-Tetra-arsenanes, 31 -

Chapter 49. Compounds with Six-Membered Heterocyclic Rings containing One or Mor eUnusual Hetero Atoms together with Nitrogen or Elements of Group VI

by R. S . EDMUNDSO N

1 . Aluminium and boron compounds 33

a . Oxa- and thia-borin g 3 6

(i) Benz- and dibenz-[1,2]oxaborins ; dibenzo[1,2]thiaborin, 36 - (ii) 3,4-Dihydro -1,2-benzoxaborins, 38 - (iii) 1,2-Oxaluminanes ; 1,2-oxaborinanes, 38 - (iv) Di-benz[1,4]oxaborins, 39 - (v) 1,4-Oxa- and 1,4-thia-borinanes, 40 -

b . Dioxaborins 40

(i) Benzo- and dibenzo-[1,3,2]dioxaluminins and -[1,3,2]dioxaborins, 40 -(ii) 1,3,2-Dioxa- and 1,3,2-dithia-borinanes ; 1 .3,2-oxaoxoniaborata salts, 40 -

c . Dibenz[2.1 .3]oxadiborins 46d . Dioxadiborins

46

(i) 1,4,2,3-Dioxadiborins, 46 - (ii) 1,4,2,5-Dioxaborinanes, 46 -

e. Trioxadiborinanes 47f. Azalumines and azaborines 47

(i) 1,2-Dihydro-1,2-azaborines ; perhydro-1,2-azaborines ; 1,2-dihydrobenz[c] -azaborines ; 1,2-azaborino[1,2-01,2]azaborine; 1,2,3,4-tetrahydro-2,l-benz[c] -azaborine, 47 - (ii) 1,2-Dihydrodibenz[c,e][1 .2]azaluminine ; 1,2-dihydrodibenz -[c,e][1,2]azaborine, 50 - (iii) Polybenzazaborines, 53 - (iv) 5,10-Dihydrodibenz -[1,4]azaborine, 56 -

g . Diazaluminines and diazaborines 5 6

(i) 1,2,3-Diazaborines and 2,3,1-benzodiazaborines, 56 - (ii)1,3,2-Diazaluminines ;1,3,2-diazaborines, perhydro derivatives and benzologues, 58 - (iii) 1,3,4-Diaza-borines, 60 -

h . Triazaborines 61i . Azadiborines 61j . Diazadialuminines and diazadiborines, and their benzologues 62

(i) 1,4,2,3-Diazadiborines and 1,2,3,6-diazadiborines, 62 - (ii) 1,2,3,4-Tetra-hydro[1,3 .2,4]benzodiazadiborine, 62 - (iii) Perhydro-1,4,2,5-diazadialumininesand -1,4,2,5-diazadiborines, 63 -

k . Triazadiborines 63

2. Silicon, germanium, tin and lead compounds 64a . Oxa-silins, -germanins and -stannins and their thia analogues 64

(i) 1,2-Oxasilins, benz[1,2]oxasilins and dibenz[1,2loxasilins, 64 - (ii) Perhydro -1,2-oxasilins (1,2-oxasilacyclohexanes) and their germanium analogues, 64 -(iii) Perhydro-l,3-oxasilins and perhydro-l,3-thiasilins (1,3-oxasila- and 1,3 -thiasila-cyclohexanes), 65 - (iv) Dibenz[1,4]oxasilins, -germanins, and -stannins ,and their thia analogues, 66 - (v) Perhydro-1,4-oxasilins (1,4-oxasilacyclohexanes )and germanium analogues, 69 -

b . Dioxasilins, dioxagermanins, dioxastannins and their thia analogues . . .

69

(i) Benzo- and dibenzo-[1,3,2]dioxasilins and analogues, 69 - (ii) Perhydro-1,3,2-dioxa-silins (I,3,2-dioxasilacyclohexanes), -germanins, -stannins, -plumbins ,titanins, and -zirconins and their thia analogues, 71 - (iii) 1,4,2-Benzodioxasilins ;1,4,2-benzodioxagermanins, 75 - (iv) Perhydro-1,4,2-dioxasilins (1,4,2-dioxasila-cyclohexanes), 1,4,2-dioxagermacyclohexanes and their thia analogues, 76 -(v) 1,3,4-Dioxagermacyclohexanes, 76 - (vi) 1,2,6-Oxathiasila- and 1,2,6-oxathia-germa-cyclohexane, 77 -

c. Trioxasilacyclohexanes ; trithiastannacyclohexanes 77d . Oxadisilins, oxadigermanins and thia analogues 7 8

(i) 2,1,3-Benzoxadisilins and related compounds, 78 - (ii) 1,2,6-Oxadisila-, 1,2,6-oxadigerma-cyclohexanes and thia analogues . 78 -

e. Dioxadisilins, dioxagermasilins and dioxadigermalins 8 0

(i) 1 .4,2,5- and 1,4,2,6-Dioxadisilacyclohexanes, 80 - (ii) l,2,4,6-Oxathiadisila-cyclohexane, 82 - (iii) 1,4,2,3-Dioxadigermacyclohexanes, 82 -

f. Oxa- and dioxa-trisilacyclohexanes 8 2g. Azasilines 8 3

(i) Dibenz[1,2]azasilines, 83 - (ii) Perhydro-l,2-azasiline (1,2-azasilacyclohexane) ,83 -(iii) Benz[d][1,3]azasilines, 84 - (iv) Perhydro-l,3-azasilines (1,3-azasilacyclo -hexanes), 84 - (v) Dibenz[1,4]aza-silines, -germanines . -stannines and -plumbines ,85 -

h. Diazasilines ; diazastannines 87

(i) Perhydro-1,3,2-diazasilines (1,3,2-diazasilacyclohexanes) and their ti nanalogues and benzologues, 87 - (ii) 1,4,2-Benzodiazasilines ; perhydro-1,4,2-diazasilines, 88 -

i. Triazasilines 8 8j. Azadisilines 8 8k. Diazadisilines and analogues 8 9

(i) Perhydro-1,2,3,6-diazadisilines, 89 - (ii) Perhydro-1,4,2,5-diazadisilines an d-1,4,2,6-diazadisilines, 89 -

1 . Triazasilines and diazatrisilines 9 1

3 . Phosphorus, arsenic and antimony compounds 9 2a. Oxaphosphorins, oxarsenins and their thia-analogues 9 2

(i) Dibenz[1,2]oxaphosphorins, 92 - (ii) Partially reduced 1,2-oxaphosphorinsand 1,2-thiaphosphorins, 92 - (iii) Perhydro-1,2-oxaphosphorins (1,2-oxaphos-phorinanes) and 1,2-oxarsenanes and their analogues . 94 - (iv) Perhydro-1,3-oxa-phosphorins (1,3-oxaphosphorinanes) and their analogues, 95 - (v) 1,4-Dihydro -1,4-oxaphosphorins, 1 .4-dihydro-1,4-thia(selena, tellura)phosphorins and thei rarsenic analogues, 95 - (vi) Dibenz[1,4]-oxaphosphorins, -oxarsenin, -oxantimoni nand their thia analogues, 98 - (vii) Tetrahydro-1,4-oxaphosphorins, 1,4-Oxa-phosphorinanes and 1,4-thiaphosphorinanes and their arsenic analogues, 103 -

b. Dioxaphosphorins, dioxarsenins, dioxantimonins and their thia analogues

104

(i) 4H-1,3,2-Dioxaphosphorins, 4H-1,3,2-benzodioxaphosphorins, 4H-1,3,2-benzarsenins, dibenzo[1,3,2]dioxaphosphorins, 104 - (ii) 1,3,2-Dioxaphosphor -inanes, -arsenanes, and -antimonanes, and their thia analogues, 106 - (iii) 1,3,2-Dioxaphosphorinanes with cage structures ; arsenic and antimony analogues . 11 2- (iv) 1,4,2-Dioxaphosphorins and their benzo derivatives, 114 - (v) 1,3,5- an d1,4,2-Dioxaphosphorinanes ; 3,5,8-trioxa-l-phosphabicyclo[2 .2 .2loctanes, 115 -

c. Perhydro-oxadiphosphorins (oxadiphosphorinanes) 11 6d. Dioxadiphosphorinanes and their arsenic analogues 11 6

(i) 1,4,2,5-Dioxadiphosphorinanes and 1,4,2,5-dioxadiarsenanes . 116 - (ii) 2,6,7-Trioxa-1,4-diphosphabicyclo[2 .2.2loctane and analogues . 117 -

e. Azaphosphorines and their arsenic analogues 11 8

(i) Dibenz[1,2]azaphosphorines, 118 - (ii) Perhydro-1,2-azaphosphorines, 118 -(iii) Tetrahydrobenz[e][1 .3]azaphosphorines, 119 - (iv) Perhydro-1,3-azaphos-phorines, 119 - (v) 1,4-Azaphosphorines and 1,4-dihydro-1,4-azaphosphorines ,119 - (vi) Dibenz[1,4]azaphosphorine and dibenz[1,4lazarsenine, 120 - (vii )Perhydro-1,4-azaphosphorines and perhydro-1,4-azarsenines, 124 -

f. Diazaphosphorines 12 6

(i) 1 .3 .2-Diazaphosphorines, 126 - (ii) Benzo[1,3,2]diazaphosphorines and relate dcompounds, 127 - (iii) Tetrahydro-1,3,2-diazaphosphorines and oxaza analogues

and their benzologues, 127 - (iv) Perhydro-1,3,2-diazaphosphorines and thei r1,3,2-oxaza and 1,3,2-thiaza analogues . 128 - (v) 1,2,4- and 1 .3,4-Diazaphos-phorines ; perhydro-1,2,4-diazaphosphorines, 131 - (vi) Perhydro-1,3,5-diaza -phosphorines, 133 -

g. Triazaphosphorines 13 3

(i) 1,3,5 .2-Triazaphosphorines, 133 - (ii) 1,2,4,5-Triazaphosphorines, 134 -(iii) Perhydro-1,2 .4,3-triazaphosphorines and -1,3,4.2-oxadiazaphosphorines,135 -

h. Perhydrotetra-aza-phosphorines and -arsenines 13 5i . Diaza- and triaza-diphosphorines ; diazatriphosphorines; diazatriarsenines

13 5

4 . Halogen compounds 13 6

Chapter 50 . Compounds with Larger Heterocyclic Rings : Seven-Membered Ring Compoundswith an Element from Group VI in the Ring

by J. M. F. GAGA N

1 . General introduction to heterocyclic compounds with rings comprising seve nor more atoms 139a . Nomenclature 14 1

2. Seven-membered heterocyclic compounds with oxygen in the ring 142a. Monocyclic compounds with one oxygen atom

142

(i) Synthesis, 142 - (ii) Structure and reactions, 143 -

b. Bicyclic compounds including an oxepin ring 149c. Oxepins with two or more annellated ring systems 15 7d. Seven-membered heterocyclic ring compounds containing two or mor e

oxygen atoms in the ring 164(i) 1,2-Dioxepins, 164 - (ii) 1,3-Dioxepins, 165 - (iii) 1,4-Dioxepins, 167 -(iv) Trioxepins . 170 -

3 . Heterocyclic seven-membered ring compounds containing sulphur 17 0a. Compounds with a single sulphur atom in the ring

17 0

(i) Thiepin derivatives, 170 -

b. Thiepins with annellated rings 17 5c. Seven-membered rings containing two or more sulphur atoms 18 6

(i) 1,2-Dithiepins, 186 - (ii) 1,3-Dithiepins, 187 - (iii) 1,4-Dithiepins . 188 -(iv) Trithiepins, 189 -

4 . Heterocyclic seven-membered ring compounds containing selenium 19 1

Chapter 51. Compounds with Larger Heterocyclic Rings : Seven-Membered Ring Compoundswith an Atom from Group V of the Periodic Table in the Ring . Nitroge n

by J. M. F . GAGA N

1 . Seven-membered rings containing a nitrogen atom 19 5a. 1H-Azepines 19 5

(i) Methods of synthesis, 195 - (ii) Structure . 198 - (iii) Reactions, 198 -

b. 2H-Azepines 201

c. 3H-Azepines

202

(i) Methods of synthesis, 202 - (ii) Reactions. 203 -

d. 4H-Azepines 204e. Dihydroazepines 20 5f. Tetrahydroazepines 20 8

(i) Tetrahydroazepinones, 209 - (ii) Caprolactim ethers and related compounds .210 -

g. Perhydroazepine (azepane, hexamethyleneimine, azacycloheptane) and it sderivatives 212

(i) Methods of synthesis, 212 - (ii) Syntheses of perhydroazepin-2-ones (e-caprolactams), 216 -

2 . Bicyclic compounds including an azepine ring 220a. Azepines fused to three-, four- or five-membered rings 220

(i) Homoazepines, 220 - (ii) Aza-azulenes. 221 -b. 1-Benzazepines 22 3c. 2-Benzazepines 22 8d. 3-Benzazepines 230e. Other azepines with one fused ring 232

3 . Azepines with two or more annellated ring systems 23 3a . Dibenzazepines 23 3

(i) Dibenz[b,d]azepines, 233 - (ii) Dibenz[b,e]azepines, 233 - (iii) Dibenz[b.f]-azepines, 235 - (iv) Dibenz[c,e]azepines, 237 - (v) Benzpyridazepines, 238 -(vi) Tribenzazepine. 239 -

4 . Seven-membered rings containing two nitrogen atoms 23 9a. Diazepines and related compounds 239

(i) 1,2-Diazepines . 239 - (ii) 1,2-Diazepines with annellated benzene rings, 247 -(iii) 1 .3-Diazepines, 250 - (iv) 1 .3-Diazepines with annellated benzene rings, 252 -(v) 1 .4-Diazepines. 256 -(vi) 1,4-Benzodiazepines, 261-(vii) 1,5-Benzodiazepines ,270 -

b. Azepines and diazepines of medicinal value 27 6

5 . Seven-membered rings containing three or more nitrogen atoms 27 7

Chapter 52. Compounds with Larger Heterocyclic Rings : Seven-Membered Ring Compoundswith Two or More Different Elements in the Ring

by J. M. F. GAGA N

1 . Rings containing oxygen and nitrogen 28 3a. Oxazepines 28 3

(i) 1,2-Oxazepines, 283 - (ii) 1,3-Oxazepines, 284 - (iii) 1,4-Oxazepines . 286 -

b. Oxadiazepines 29 0

2 . Rings containing oxygen and sulphur 29 2

3 . Rings containing nitrogen and sulphur 294a. Thiazepines 294

(i) 1,2- and 1,3-thiazepines. 294 - (ii) 1 .4-Thiazepines, 296 - (iii) 1,5-Thiazepines ,301 - (iv) Benzothiazepines, 303 -

b. Thiadiazepines 306c. Dithiazepines 31 1

4. Rings containing nitrogen and selenium 31 2

5. Rings containing nitrogen, oxygen and sulphur 31 2

Chapter 53 . Compounds with Seven-Membered and Larger Rings possessing One or MoreUnusual Hetero Atoms

by R. S . EDMUND SO N

1 . Magnesium and mercury compounds 31 5

2 . Boron compounds 31 7a. Unsaturated systems containing boron ; borepins 31 7b. Saturated systems ; borepanes and related compounds 31 9

3 . Silicon, germanium, tin and lead compounds 32 1a. Compounds with one hetero atom 32 1

(i) Seven-membered ring compounds, 321 - (ii) Larger ring compounds, 323 -(iii) Polycyclic compounds, 325 -

b. Compounds with two hetero atoms 33 1c. Compounds with three or more hetero atoms 334

4. Phosphorus and arsenic compounds 33 6a. Compounds containing one hetero atom 337

(i) Phosphepins and related compounds, 337 - (ii) Phosphocins, 340 - (iii) Higherphosphacycloalkenes and related compounds, 341 - (iv) Phosphepanes andrelated compounds, 341 - (v) Phosphabicyclo-alkanes and -alkenes and relate dcompounds, 342 -

b. Compounds with two hetero atoms 34 3c. Compounds with three or more hetero atoms 34 6

5 . Iodine compounds 347

Chapter 54. Compounds with Seven-Membered and Larger Rings containing One or MoreAtoms of Unusual Hetero Elements together with Nitrogen or Elements of Group VI

by R . S. EDMUNDSO N

1 . Mercury compounds 349

2 . Aluminium and boron compounds 34 9a. Compounds containing oxygen and/or sulphur as additional elements 349b. Compounds containing nitrogen as the additional element 35 2c. Compounds containing nitrogen together with oxygen and/or sulphur as

additional elements 35 4

3 . Silicon, germanium and tin compounds 35 6a . Compounds containing oxygen and/or sulphur as additional elements 35 6

(i) Oxasila compounds and germanium and tin analogues, 356 - (ii) Di-, tri- andtetra-oxasilepins and related compounds, 359 - (iii) Oxadisilepins etc. . 364 -

b. Compounds with nitrogen as the additional element 37 1

f) Azasilepines and related compounds, 371 - (II) Azapolysilepines and relate dcompounds, 373 -

c. Compounds containing nitrogen together with oxygen as additional elements 37 3

4 . Phosphorus, arsenic and antimony compounds 374a. Compounds containing oxygen and/or sulphur as additional element 374b. Compounds containing nitrogen as the additional element 379c. Compounds containing nitrogen together with Group VI elements 382

5. The "atranes" 384

Chapter 55 . Compounds with Larger Heterocyclic Rings : Eight-Membered Ring Compoundsby J . M . F. GAGA N

1 . Eight-membered ring compounds containing oxygen 38 7a. With rings containing one oxygen atom

38 7

(i) Derivatives of oxocin, 387 - (ii) Benzoxocins, 389 -

b. Eight-membered ring compounds containing two or more oxygen atoms . 390

(i) Dioxocins and their derivatives, 390 - (ii) Trioxocane and tetraoxocanes, 393 -

2 . Eight-membered rings containing sulphur or selenium 394a. Compounds containing one sulphur atom 394b. Compounds containing two or more sulphur atoms 39 5

(i) Dithiocins and related compounds, 395 - (ii) Compounds with more than twoatoms of sulphur, 398 -

3 . Eight-membered ring compounds containing nitrogen 399a . Compounds containing a single nitrogen atom 399

(i) Azocine and its derivatives . 400 - (ii) Azocines with one annellated ring, 404 -(iii) Azocines with more than one annellated ring, 408 -

b . Eight-membered ring compounds containing two nitrogen atoms . . . .

41 1

(i) 1,2-Diazocines, 411 - (ii) 1,3-Diazocines, 413 - (iii) 1,4-Diazocines, 414 -(iv) 1,5-Diazocines, 418 -

c. Eight-membered rings containing three or more nitrogen atoms

423

(i) Triazocine derivatives, 423 - (ii) Tetrazocine derivatives, 424 -

Chapter 56. Compounds with Larger Heterocyclic Rings : Compounds with Rings of Morethan Eight Atoms

by J . M . F. GAGA N

1 . Nine-membered ring compounds 42 7a. Nine-membered ring compounds containing oxygen 42 7

(i) Oxonins, 427 - (ii) Dioxonins, 429 - (iii) Ring compounds with three or moreatoms in the ring, 430 -

b. Nine-membered ring compounds containing sulphur 431

c. Nine-membered ring compounds containing nitrogen 432

(i) Rings containing one nitrogen atom, 432 - (ii) Nine-membered rings con-taining more than one nitrogen atom . 437 -

2. Ten-membered ring compounds 440a. Ten-membered ring compounds containing oxygen 440

(i) Compounds with one heterocyclic oxygen atom . 440 - (ii) Compounds withtwo or more heterocyclic oxygen atoms, 441 -

b. Ten-membered ring compounds containing sulphur or selenium 442

(0 Compounds with one atom in the heterocycle, 442 - (ii) Compounds withtwo or more heteroatoms in the ring, 443 -

c. Ten-membered rings containing nitrogen 44 4

(i) Compounds containing one heterocyclic nitrogen atom, 444 - (ii) Compoundscontaining two nitrogen atoms in the heterocyclic ring, 446 -

3 . Rings with more than ten atoms 448a. Large rings containing oxygen 449

(i) Lactones, 449 - (ii) Cyclic esters, diol carbonates and anhydrides, 451 -(iii) Cyclic ethers, 452 - (iv) Macrocyclic polyethers . 453 - (v) Macrolide anti-biotics, 455 -

b. Large rings containing sulphur or selenium 456

c. Large rings containing nitrogen . .

. 45 8(1) Rings with one nitrogen atom, 458 - (ii) Rings with two nitrogen atoms. 460 -(iii) Rings with more than two nitrogen atoms . 462 -

Index 467