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