Organic Chemistry of Explosives

Organic Chemistry of Explosives is the first text to bring together the essential methods and routes used for the synthesis of organic explosives in a single volume. Assuming no prior knowledge, the book discusses everything from the simplest mixed acid nitration of toluene, to the complex synthesis of highly energetic caged nitro compounds. Reviews laboratory and industrial methods, which can be used to introduce aliphatic C-nitro, aromatic C-nitro, N-nitro, and nitrate ester functionality into organic compounds Discusses the advantages and disadvantages of each synthetic method or route, with scope, limitations, substrate compatibility and other important considerations Features numerous examples in the form of text, reaction diagrams, and tables.

Jai Prakash Agrawal is the former Director of Materials of the Indian Defence Research and Development Organization. He obtained his PhD in Chemistry from the Gorakhpur University, India, and did postdoctoral work at the University of Saint-Etienne, France, and at the Cavendish Laboratory of the University of Cambridge, UK. In recognition of his achievements Dr. Agrawal was appointed a Fellow of the Royal Society of Chemistry, London. The focus of his scientific and professional career is on research and development in the field of propellants, explosives and inhibitory materials. He has written a monograph on "Composite Materials" and is recipient of several honours including the prestigious DRDO Technology Award. Together with Robert Hodgson he has authored the book "Organic Chemistry of Explosives", John Wiley & Sons.

Foreword	p. xi
Preface	p. xiii
Abbreviations	p. xv
Acknowledgements	p. xxiii
Background	p. xxv
Synthetic Routes to Aliphatic C-Nitro Functionality	p. 1
Introduction	p. 1
Aliphatic C-nitro compounds as explosives	p. 2
Direct nitration of alkanes	p. 2
Addition of nitric acid, nitrogen oxides and related compounds to unsaturated bonds	p. 3
Nitric acid and its mixtures	p. 3
Nitrogen dioxide	p. 4
Dinitrogen pentoxide	p. 5
Nitrous oxide and dinitrogen trioxide	p. 6
Other nitrating agents	p. 6
Halide displacement	p. 7
Victor Meyer reaction	p. 7
Modified Victor Meyer reaction	p. 9
Ter Meer reaction	p. 10
Displacements using nitronate salts as nucleophiles	p. 13
Oxidation and nitration of C-N bonds	p. 14
Oxidation and nitration of oximes	p. 14
Oxidation of amines	p. 19
Nitration of nitronate salts	p. 21
Oxidation of pseudonitroles	p. 23
Oxidation of isocyanates	p. 23
Oxidation of nitrosoalkanes	p. 24
Kaplan-Shechter reaction	p. 24
Nitration of compounds containing acidic hydrogen	p. 27
Alkaline nitration	p. 27
Acidic nitration	p. 31
Oxidative dimerization	p. 32
Addition and condensation reactions	p. 33
1,2-Addition reactions	p. 33
1,4-Addition reactions	p. 35
Mannich reaction	p. 43
Henry reaction	p. 44
Derivatives of polynitroaliphatic alcohols	p. 46
Miscellaneous	p. 49
1,1-Diamino-2,2-dinitroethylenes	p. 49
Other routes to aliphatic nitro compounds	p. 50
Selective reductions	p. 51
Chemical stability of polynitroaliphatic compounds	p. 51
Reactions with mineral acids	p. 52
Reactions with base and nucleophiles	p. 52
References	p. 55
Energetic Compounds 1: Polynitropolycycloalkanes	p. 67
Caged structures as energetic materials	p. 67
Cyclopropanes and spirocyclopropanes	p. 68
Cyclobutanes and their derivatives	p. 69
Cubanes	p. 71
Homocubanes	p. 74
Prismanes	p. 78
Adamantanes	p. 79
Polynitrobicycloalkanes	p. 82
Norbomanes	p. 82
Bicyclo[3.3.0]octane	p. 84
Bicyclo[3.3,1]nonane	p. 85
References	p. 85
Synthetic Routes to Nitrate Esters	p. 87
Nitrate esters as explosives	p. 87
Nitration of the parent alcohol	p. 90
O-Nitration with nitric acid and its mixtures	p. 90
O-Nitration with dinitrogen tetroxide	p. 93
O-Nitration with dinitrogen pentoxide	p. 93
O-Nitration with nitronium salts	p. 94
Transfer nitration	p. 95
Other O-nitrating agents	p. 96
Nucleophilic displacement with nitrate anion	p. 97
Metathesis between alkyl halides and silver nitrate	p. 97
Decomposition of nitratocarbonates	p. 98
Displacement of sulfonate esters with nitrate anion	p. 98
Displacement with mercury (I) nitrate	p. 99
Nitrate esters from the ring-opening of strained oxygen heterocycles	p. 99
Ring-opening nitration of epoxides	p. 99
1,3-Dinitrate esters from the ring-opening nitration of oxetanes with dinitrogen pentoxide	p. 102
Other oxygen heterocycles	p. 103
Nitrodesilylation	p. 103
Additions to alkenes	p. 104
Nitric acid and its mixtures	p. 104
Nitrogen oxides	p. 105
Metal salts	p. 106
Halonitroxylation	p. 106
Deamination	p. 106
Miscellaneous methods	p. 107
Synthetic routes to some polyols and their nitrate ester derivatives	p. 108
Energetic nitrate esters	p. 112
References	p. 117
Synthetic Routes to Aromatic C-Nitro Compounds	p. 125
Introduction	p. 125
Polynitroarylenes as explosives	p. 126
Nitration	p. 128
Nitration with mixed acid	p. 129
Substrate derived reactivity	p. 131
Effect of nitrating agent and reaction conditions on product selectivity	p. 138
Other nitrating agents	p. 139
Side-reactions and by-products from nitration	p. 143
Nitrosation-oxidation	p. 144
Nitramine rearrangement	p. 145
Reaction of diazonium salts with nitrite anion	p. 148
Oxidation of arylamines, arylhydroxylamines and other derivatives	p. 149
Oxidation of arylamines and their derivatives	p. 149
Oxidation of arylhydroxylamines and their derivatives	p. 155
Nucleophilic aromatic substitution	p. 157
Displacement of halide	p. 158
Nitro group displacement and the reactivity of polynitroarylenes	p. 167
Displacement of other groups	p. 169
Synthesis of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)	p. 172
The chemistry of 2,4,6-trinitrotoluene (TNT)	p. 174
Conjugation and thermally insensitive explosives	p. 176
References	p. 180
Synthetic Routes to N-Nitro Functionality	p. 191
Introduction	p. 191
Nitramines, nitramides and nitrimines as explosives	p. 192
Direct nitration of amines	p. 195
Nitration under acidic conditions	p. 195
Nitration with nonacidic reagents	p. 202
Nitration of chloramines	p. 207
Nitration of dialkylchloramines	p. 207
Nitration of alkyldichloramines	p. 207
N-Nitration of amides and related compounds	p. 208
Nitration with acidic reagents	p. 208
Nitration with nonacidic reagents	p. 211
Nitrolysis	p. 213
Nitrolysis of amides and their derivatives	p. 213
Nitrolysis of N-alkyl bonds	p. 217
Nitrolysis of nitrosamines	p. 221
Nitrative cleavage of other nitrogen bonds	p. 223
Ring-opening nitration of strained nitrogen heterocycles	p. 225
Aziridines	p. 226
Azetidines	p. 227
Nitrosamine oxidation	p. 228
Hydrolysis of nitramides and nitroureas	p. 229
Dehydration of nitrate salts	p. 232
Other methods	p. 233
Primary nitramines as nucleophiles	p. 234
1,4-Michael addition reactions	p. 234
Mannich condensation reactions	p. 235
Condensations with formaldehyde	p. 239
Nucleophilic displacement reactions	p. 240
Aromatic nitramines	p. 240
The nitrolysis of hexamine	p. 240
The synthesis of RDX	p. 243
The synthesis of HMX	p. 247
Effect of reaction conditions on the nitrolysis of hexamine	p. 250
Other nitramine products from the nitrolysis of hexamine	p. 252
References	p. 255
Energetic Compounds 2: Nitramines and Their Derivatives	p. 263
Cyclopropanes	p. 263
Cyclobutanes	p. 264
Azetidines - 1,3,3-trinitroazetidine (TNAZ)	p. 265
Cubane-based nitramines	p. 268
Diazocines	p. 269
Bicycles	p. 271
Caged heterocycles - isowurtzitanes	p. 273
Heterocyclic nitramines derived from Mannich reactions	p. 276
Nitroureas	p. 277
Other energetic nitramines	p. 282
Energetic groups	p. 284
Dinitramide anion	p. 284
Alkyl N,N-dinitramines	p. 286
N-Nitroimides	p. 287
References	p. 288
Energetic Compounds 3: N-Heterocycles	p. 293
Introduction	p. 293
5-Membered rings - 1N - pyrroles	p. 294
5-Membered rings - 2N	p. 294
Pyrazoles	p. 294
Imidazoles	p. 296
1,3,4-Oxadiazoles	p. 297
1,2,5-Oxadiazoles (furazans)	p. 297
Benzofurazans	p. 302
Furoxans	p. 302
Benzofuroxans	p. 303
5-Membered rings - 3N	p. 307
Triazoles	p. 307
Triazolones	p. 312
Benzotriazoles	p. 313
5-Membered rings - 4N	p. 314
6-Membered rings - 1N - pyridines	p. 317
6-Membered rings - 2N	p. 318
6-Membered rings - 3N	p. 320
6-Membered rings - 4N	p. 321
Dibenzotetraazapentalenes	p. 324
References	p. 326
Miscellaneous Explosive Compounds	p. 333
Organic azides	p. 333
Alkyl azides	p. 333
Aromatic azides	p. 338
Peroxides	p. 339
Diazophenols	p. 340
Diazophenols from the diazotization of aminophenols	p. 340
Diazophenols from the rearrangement of o-nitroarylnitramines	p. 341
Nitrogen-rich compounds from guanidine and its derivatives	p. 343
References	p. 346
Dinitrogen Pentoxide - An Eco-Friendly Nitrating Agent	p. 349
Introduction	p. 349
Nitrations with dinitrogen pentoxide	p. 350
The chemistry of dinitrogen pentoxide	p. 351
Preparation of dinitrogen pentoxide	p. 351
C-nitration	p. 353
W-nitration	p. 355
Nitrolysis	p. 357
O-nitration	p. 359
Ring cleavage nitration	p. 360
Selective O-nitration	p. 361
Glycidyl nitrate and NIMMO - batch reactor verses flow reactor	p. 362
Synthesis of the high performance and eco-friendly oxidizer - ammonium dinitramide	p. 363
References	p. 364
Index	p. 367
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Organic Chemistry of Explosives

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