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

RODD'S CHEMISTRY O F

CARBON COMPOUND S

A modern comprehensive treatise

Edited byMARTIN F. ANSELL

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

Queen Mary College, University ofLondon, Great Britai n

Supplement to

VOLUME IV HETEROCYCLIC COMPOUND S

PART C :

Five-Membered Heterocyclic Compounds wit hTwo Hetero-Atoms in the Ring from Groups V and/or V I

of the Periodic Tabl e

PART D :

Five-Membered Heterocyclic Compounds with More thanTwo Hetero-Atoms in the Ring

VOLUME IV C and D

Heterocyclic Compounds : Five-membered Heterocyclic Compounds with Two Hetero -atoms in the Ring from Groups V and/or VI of the Periodic Tabl e

Five-membered Heterocyclic Compounds with More than Two Hetero-atoms in the Rin g

List of contributors viPreface vi iOfficial publications ; scientific journals and periodicalsList of common abbreviations and symbols used

Chapter 16. Five-membered Heterocyclic Compounds wit hTwo Nitrogen Atoms in the Ring

by S .T . MULLIN S

1 . Pyrazole 1(a) Preparation 1(b) Cyclisation 1(c) From other heterocycles 1 1(d) Pyrazole derivatives

1 1(i) N-oxides, 11 - (ii) N-alkyl and N-aryl derivatives, 11 - (iii) N-acylderivatives, 13 - (iv) C-alkyl and C-aryl derivatives, 1 6

(e) Fused systems 1 8(f) Reduced systems 2 1

2 . Indazoles 25(a) Preparation 25(b) From benzoid precursors 25(c) Miscellaneous 32(d) Indazole derivatives

33(i) Alkyl and aryl derivatives, 33 - (ii) Carboxylic acid derivativesand indazolediones, 34 - (iii) Aminoindazoles, 36 - (iv) Halogenatedindazoles, 36 -

(e) Fused systems

3 7(i) Pyrazoloindazoles, 37 - (ii) Triazoloindazoles, 39 - (iii) Benzinda-zoles, 41 -

(f) Reduced indazoles 4 13 . Imidazoles 43

(a) Preparation 43(b) Cyclisation 44(c) Other cyclisation reactions 49(d) From other heterocycles 52

(e) Imidazole derivatives

5 3(i) N-substituted derivatives, 53 - (ii) C-alkyl- and C-arylimidazoles ,55 - (iii) Halogenated derivatives, 58 - (iv) Nitrogen derivatives, 62 - (v )Sulphur derivatives, 64 - (iv) Metalloimidazoles, 64 -

(1) Miscellaneous 6 6(g) Fused imidazoles 6 8(h) Reduced imidazoles 7 6

4 . Benzimidazoles 7 9(a) Synthesis 7 9(b) Benzimidazole derivatives 8 3

(i) N-oxides, 83 - (ii) N-alkyl derivatives, 84 - (iii) C-alkyl derivatives,85 - (iv) Amino derivatives, 87 - (v) Sulphur containing derivatives ,90 - (vi) Aldehydes and ketones, 91 -

(c) Fused benzimidazole derivatives 9 2

Chapter 17. Five-membered Heterocyclic Compounds withTwo Different Hetero-atoms in the Ring

by J .D . HEPWORTH and M. WAINWRIGH T

1 . Isoxazole and its derivatives 95(a) Isoxazoles

96(i) Synthesis, 96 - (ii) Reactions, 10 7

(b) Reduced Systems

11 5(i) Synthesis of isoxazolines, 115 - (ii) Synthesis of isoxazolidines, 123 -(iii) Reactions of isoxazolines and isoxazolidines, 127 -

2 . Benzisoxazoles 129(a) 1,2-Benzisoxazoles (Indoxazenes)

130(i) Synthesis, 130 - (ii) Properties and reactions, 131 -

(b) 2,1-Benzisoxazoles (Anthranils)

13 3(i) Synthesis, 133 - (ii) Reactions, 137 -

3 . Oxazole and its derivatives 14 1(a) Oxazoles

142(i) Synthesis, 142 - (ii) Reactions, 151 -

(b) Reduced systems 162Benzoxazoles 174(a) Synthesis 174(b) Reactions 18 1

5 . Isothiazole and its derivatives 18 4(a) Isothiazoles

18 4(i) Synthesis, 184 - (ii) Reactions, 188 -

6. Benzisothiazoles 19 2(a) Synthesis 19 2(b) Synthesis of benzisothiazole-1,1-dioxides 19 4(c) Reactions 196(d) Reactions of saccharin 200

7. Thiazole and its derivatives 205(a) Thiazoles

205(i) Synthesis, 205 - (ii) Reactions, 215 -

(b) Thiazolinethiones 222

(c) Thiazolidines 22 5(d) Reactions of the thiazole system yielding fused heterocycles

22 7(i) Oxygen- and sulphur-containing fused thiazoloheterocycles, 227 -

(e) Nitrogen-containing fused thiazoloheterocycles 229(i) 5-Membered fused rings containing one nitrogen atom, 229 -(ii) 5-Membered fused rings containing two nitrogen atoms, 230 -(iii) 5-Membered fused rings containing three nitrogen atoms, 232 -(iv) 6-Membered fused rings containing one nitrogen atom, 233 -(v) 6-Membered fused rings containing two nitrogen atoms, 234 -(vi) 6-Membered fused rings containing three nitrogen atoms, 235 -(vii) Larger nitrogen-containing fused rings, 236 -

8 . Benzothiazoles 23 7(a) Synthesis 23 7(b) Reactions 24 1

9 . Isoselenazoles 24810 . Benzisoselenazoles 249

(a) Synthesis 249(b) Reactions 25 0

11 . Isotellurazoles and benzisotellurazoles 25 212 . Selenazoles 25 3

(a) Synthesis 25 3(b) Reactions 25 4(c) Fused heterocyclic selenazoles 25 5

13 . Benzoselenazoles 25 614 . Benzotellurazoles 25 7

Chapter 18. Five-membered Heterocyclic Compounds wit hThree Hetero-atoms in the Ring

by D.J . ROWE

1 . Introduction 2592 . 1,2,3-Triazoles 259

(a) Synthesis of 1,2,3-triazoles

259(i) 1,3-Dipolar addition reactions, 259 -

(b) Oxidative synthesis 264(c) Reactions and uses of 1,2,3-triazoles 265(d) Extrusion of nitrogen from benzotriazoles 269

3 . Triazolines 278(a) Synthesis of triazolines

279(i) 1,3-Dipolar addition of azides to alkenes, 279 -

4. 1,2,4-Triazoles 285(a) Synthesis

285(i) By cycloaddition, 296 -

(b) Reactions 2975 . 1,2,3-Oxadiazoles 2986 . 1,2,4-Oxadiazoles 299

(a) Synthesis 29 9(b) 1,3-Dipolar cycloaddition methods 29 9(c) Other methods 306

(d) Reactions 30 77 . 1,3,4-Oxadiazoles 30 9

(a) Synthesis 30 9(b) From acyl hydrazides 30 9(c) Oxidative methods 31 1(d) Other methods 31 3(e) Reactions of 1,3,4-oxadiazoles 31 3

8 . 1,2,5-Oxadiazoles 31 5(a) Synthesis 31 5(b) Reactions 31 7

9 . 1,2,3-Thiadiazoles 31 8(a) Synthesis and reactions 31 9

10 . 1,2,4-Thiadiazoles 32 3(a) Synthesis 32 3(b) Oxidative cyclisation 323(c) Cycloaddition of nitrite sulphides 325

11 . 1,2,5-Thiadiazoles 327(a) Synthesis 32 7(b) Reactions 330

12 . 1,3,4-Thiadiazoles 33 1(a) Synthesis

33 1(i) Oxidative cyclisation, 331 - (ii) Non-oxidative methods, 334 - (iii )Cycloaddition methods, 339 -

13 . Selenadiazoles 34 1(a) Synthesis and reactions 342

14 . Other five-membered rings with three heteroatoms 346(a) Oxathiazoles 346(b) 1,2,4-Dithiazoles 34 7(c) 1,4,2-Dithiazoles 34 7

15 . Heterocyclic rearrangements 348(a) The Dimroth rearrangement

348(i) The mechanism of the Dimroth rearrangement, 350 -- (ii) Th eDimroth rearrangement in other heterocycles, 355 -

(b) The Boulton-Katritzky scheme 360(c) Photochemical rearrangements 370

Chapter 19. Five-membered Heterocyclic Compound.: withFour Hetero-atoms in the Ring

by J .H. LITTLE

Introduction 37 51 . Tetrazoles 37 5

(a) Synthesis 37 6(b) Spectroscopic and other studies 382(c) Thermolysis and photolysis 38 5(d) Other reactions 388

(e) Applications

394(i) Pharmaceuticals, 394 - (ii) Herbicides, 395 - (iii) Polymers, 395 -(iv) Oligonucleotide synthesis, 396 -

2. Oxatriazoles 39 63. Thiatriazoles 39 9

(a) 1,2,3,4-Thiatriazoles

39 9(i) Synthesis, 399 -

(b) 1,2,3,5-Thiatriazoles 40 44. Dioxathiazoles and oxathiadiazoles 40 65. Dithiadiazoles and dioxadiazoles 40 8

(a) 1,2,3,5-dithiadiazoles 40 8(b) 1,3,2,4-Dithiadiazoles 41 1(c) Dioxadiazoles 41 4

6. Phosphorus-containing heterocycles 41 4(a) Triazaphospholes

41 4(i) 1,2,3,4-Triazaphospholes, 414 - (ii) 1,2,4,3-Triazaphospholes, 417 -

(b) Diazadiphospholanes 42 0(c) Oxadiazaphospholes 42 1(d) Thiadiazaphospholes 42 2(e) Tetraphospholanes 42 3

Index 427