Organic Chemistry of Explosives

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 page xiiiPreface xvAbbreviations xviiAcknowledgements xxvBackground xxvii1 Synthetic Routes to Aliphatic C-Nitro Functionality 11.1 Introduction 11.2 Aliphatic C-nitro compounds as explosives 21.3 Direct nitration of alkanes 21.4 Addition of nitric acid, nitrogen oxides and related compounds to unsaturated bonds 31.4.1 Nitric acid and its mixtures 31.4.2 Nitrogen dioxide 41.4.3 Dinitrogen pentoxide 51.4.4 Nitrous oxide and dinitrogen trioxide 61.4.5 Other nitrating agents 61.5 Halide displacement 71.5.1 Victor Meyer reaction 71.5.2 Modified Victor Meyer reaction 91.5.3 Ter Meer reaction 101.5.4 Displacements using nitronate salts as nucleophiles 131.6 Oxidation and nitration of C–N bonds 141.6.1 Oxidation and nitration of oximes 141.6.2 Oxidation of amines 191.6.3 Nitration of nitronate salts 211.6.4 Oxidation of pseudonitroles 231.6.5 Oxidation of isocyanates 231.6.6 Oxidation of nitrosoalkanes 241.7 Kaplan–Shechter reaction 241.8 Nitration of compounds containing acidic hydrogen 271.8.1 Alkaline nitration 271.8.2 Acidic nitration 311.9 Oxidative dimerization 321.10 Addition and condensation reactions 331.10.1 1,2-Addition reactions 331.10.2 1,4-Addition reactions 351.10.3 Mannich reaction 431.10.4 Henry reaction 441.11 Derivatives of polynitroaliphatic alcohols 461.12 Miscellaneous 491.12.1 1,1-Diamino-2,2-dinitroethylenes 491.12.2 Other routes to aliphatic nitro compounds 501.12.3 Selective reductions 511.13 Chemical stability of polynitroaliphatic compounds 511.13.1 Reactions with mineral acids 521.13.2 Reactions with base and nucleophiles 52References 552 Energetic Compounds 1: Polynitropolycycloalkanes 672.1 Caged structures as energetic materials 672.2 Cyclopropanes and spirocyclopropanes 682.3 Cyclobutanes and their derivatives 692.4 Cubanes 712.5 Homocubanes 742.6 Prismanes 782.7 Adamantanes 792.8 Polynitrobicycloalkanes 822.8.1 Norbornanes 822.8.2 Bicyclo[3.3.0]octane 842.8.3 Bicyclo[3.3.1]nonane 85References 853 Synthetic Routes to Nitrate Esters 873.1 Nitrate esters as explosives 873.2 Nitration of the parent alcohol 903.2.1 O-Nitration with nitric acid and its mixtures 903.2.2 O-Nitration with dinitrogen tetroxide 933.2.3 O-Nitration with dinitrogen pentoxide 933.2.4 O-Nitration with nitronium salts 943.2.5 Transfer nitration 953.2.6 Other O-nitrating agents 963.3 Nucleophilic displacement with nitrate anion 973.3.1 Metathesis between alkyl halides and silver nitrate 973.3.2 Decomposition of nitratocarbonates 983.3.3 Displacement of sulfonate esters with nitrate anion 983.3.4 Displacement with mercury (I) nitrate 993.4 Nitrate esters from the ring-opening of strained oxygen heterocycles 993.4.1 Ring-opening nitration of epoxides 993.4.2 1,3-Dinitrate esters from the ring-opening nitration of oxetanes with dinitrogen pentoxide 1023.4.3 Other oxygen heterocycles 1033.5 Nitrodesilylation 1033.6 Additions to alkenes 1043.6.1 Nitric acid and its mixtures 1043.6.2 Nitrogen oxides 1053.6.3 Metal salts 1063.6.4 Halonitroxylation 1063.7 Deamination 1063.8 Miscellaneous methods 1073.9 Synthetic routes to some polyols and their nitrate ester derivatives 1083.10 Energetic nitrate esters 112References 1174 Synthetic Routes to Aromatic C-Nitro Compounds 1254.1 Introduction 1254.2 Polynitroarylenes as explosives 1264.3 Nitration 1284.3.1 Nitration with mixed acid 1294.3.2 Substrate derived reactivity 1314.3.3 Effect of nitrating agent and reaction conditions on product selectivity 1384.3.4 Other nitrating agents 1394.3.5 Side-reactions and by-products from nitration 1434.4 Nitrosation–oxidation 1444.5 Nitramine rearrangement 1454.6 Reaction of diazonium salts with nitrite anion 1484.7 Oxidation of arylamines, arylhydroxylamines and other derivatives 1494.7.1 Oxidation of arylamines and their derivatives 1494.7.2 Oxidation of arylhydroxylamines and their derivatives 1554.8 Nucleophilic aromatic substitution 1574.8.1 Displacement of halide 1584.8.2 Nitro group displacement and the reactivity of polynitroarylenes 1674.8.3 Displacement of other groups 1694.8.4 Synthesis of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) 1724.9 The chemistry of 2,4,6-trinitrotoluene (TNT) 1744.10 Conjugation and thermally insensitive explosives 176References 1805 Synthetic Routes to N-Nitro Functionality 1915.1 Introduction 1915.2 Nitramines, nitramides and nitrimines as explosives 1925.3 Direct nitration of amines 1955.3.1 Nitration under acidic conditions 1955.3.2 Nitration with nonacidic reagents 2025.4 Nitration of chloramines 2075.4.1 Nitration of dialkylchloramines 2075.4.2 Nitration of alkyldichloramines 2075.5 N-Nitration of amides and related compounds 2085.5.1 Nitration with acidic reagents 2085.5.2 Nitration with nonacidic reagents 2115.6 Nitrolysis 2135.6.1 Nitrolysis of amides and their derivatives 2135.6.2 Nitrolysis of N-alkyl bonds 2175.6.3 Nitrolysis of nitrosamines 2215.7 Nitrative cleavage of other nitrogen bonds 2235.8 Ring-opening nitration of strained nitrogen heterocycles 2255.8.1 Aziridines 2265.8.2 Azetidines 2275.9 Nitrosamine oxidation 2285.10 Hydrolysis of nitramides and nitroureas 2295.11 Dehydration of nitrate salts 2325.12 Other methods 2335.13 Primary nitramines as nucleophiles 2345.13.1 1,4-Michael addition reactions 2345.13.2 Mannich condensation reactions 2355.13.3 Condensations with formaldehyde 2395.13.4 Nucleophilic displacement reactions 2405.14 Aromatic nitramines 2405.15 The nitrolysis of hexamine 2435.15.1 The synthesis of RDX 2435.15.2 The synthesis of HMX 2475.15.3 Effect of reaction conditions on the nitrolysis of hexamine 2505.15.4 Other nitramine products from the nitrolysis of hexamine 252References 2556 Energetic Compounds 2: Nitramines and Their Derivatives 2636.1 Cyclopropanes 2636.2 Cyclobutanes 2646.3 Azetidines – 1,3,3-trinitroazetidine (TNAZ) 2656.4 Cubane–based nitramines 2686.5 Diazocines 2696.6 Bicycles 2716.7 Caged heterocycles – isowurtzitanes 2736.8 Heterocyclic nitramines derived from Mannich reactions 2766.9 Nitroureas 2776.10 Other energetic nitramines 2826.11 Energetic groups 2846.11.1 Dinitramide anion 2846.11.2 Alkyl N,N-dinitramines 2866.11.3 N-Nitroimides 287References 2887 Energetic Compounds 3: N-Heterocycles 2937.1 Introduction 2937.2 5-Membered rings – 1N – pyrroles 2947.3 5-Membered rings – 2N 2947.3.1 Pyrazoles 2947.3.2 Imidazoles 2967.3.3 1,3,4-Oxadiazoles 2977.3.4 1,2,5-Oxadiazoles (furazans) 2977.3.5 Benzofurazans 3027.3.6 Furoxans 3027.3.7 Benzofuroxans 3037.4 5-Membered rings – 3N 3077.4.1 Triazoles 3077.4.2 Triazolones 3127.4.3 Benzotriazoles 3137.5 5-Membered rings – 4N 3147.6 6-Membered rings – 1N – pyridines 3177.7 6-Membered rings – 2N 3187.8 6-Membered rings – 3N 3207.9 6-Membered rings – 4N 3217.10 Dibenzotetraazapentalenes 324References 3268 Miscellaneous Explosive Compounds 3338.1 Organic azides 3338.1.1 Alkyl azides 3338.1.2 Aromatic azides 3388.2 Peroxides 3398.3 Diazophenols 3408.3.1 Diazophenols from the diazotization of aminophenols 3408.3.2 Diazophenols from the rearrangement of o-nitroarylnitramines 3418.4 Nitrogen-rich compounds from guanidine and its derivatives 343References 3469 Dinitrogen Pentoxide – An Eco-Friendly Nitrating Agent 3499.1 Introduction 3499.2 Nitrations with dinitrogen pentoxide 3509.3 The chemistry of dinitrogen pentoxide 3519.4 Preparation of dinitrogen pentoxide 3519.5 C-nitration 3539.6 N-nitration 3559.7 Nitrolysis 3579.8 O-nitration 3599.9 Ring cleavage nitration 3609.10 Selective O-nitration 3619.10.1 Glycidyl nitrate and NIMMO – batch reactor verses flow reactor 3629.11 Synthesis of the high performance and eco-friendly oxidizer – ammonium dinitramide 363References 364Index 367

"With about 1500 references and many citations leading to existing reviews and further reading, this high quality book is an indispensable reference that should find its place in every good scientific library." (SYNTHESIS, December 2007) "…fill[s] a void in the literature by authoring a reference text that provides detailed information on the synthetic routes to a wide variety of energetic materials." (Journal of Hazardous Metals, July 2007)