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- 1 Synthetic Routes to AliphaticC-Nitro Functionality Background xxv
- 1.1 Introduction
- 1.2 AliphaticC-nitro compounds as explosives
- 1.3 Direct nitration of alkanes
- bonds 1.4 Addition of nitric acid, nitrogen oxides and related compounds to unsaturated
- 1.4.1 Nitric acid and its mixtures
- 1.4.2 Nitrogen dioxide
- 1.4.3 Dinitrogen pentoxide
- 1.4.4 Nitrous oxide and dinitrogen trioxide
- 1.4.5 Other nitrating agents
- 1.5 Halide displacement
- 1.5.1 Victor Meyer reaction
- 1.5.2 Modified Victor Meyer reaction
- 1.5.3 Ter Meer reaction
- 1.5.4 Displacements using nitronate salts as nucleophiles
- 1.6 Oxidation and nitration of C–N bonds
- 1.6.1 Oxidation and nitration of oximes
- 1.6.2 Oxidation of amines
- 1.6.3 Nitration of nitronate salts
- 1.6.4 Oxidation of pseudonitroles
- 1.6.5 Oxidation of isocyanates
- 1.6.6 Oxidation of nitrosoalkanes
- 1.7 Kaplan–Shechter reaction
- 1.8 Nitration of compounds containing acidic hydrogen
- 1.8.1 Alkaline nitration
- 1.8.2 Acidic nitration
- 1.9 Oxidative dimerization
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- 1.10 Addition and condensation reactions vi Contents
- 1.10.1 1,2-Addition reactions
- 1.10.2 1,4-Addition reactions
- 1.10.3 Mannich reaction
- 1.10.4 Henry reaction
- 1.11 Derivatives of polynitroaliphatic alcohols
- 1.12 Miscellaneous
- 1.12.1 1,1-Diamino-2,2-dinitroethylenes
- 1.12.2 Other routes to aliphatic nitro compounds
- 1.12.3 Selective reductions
- 1.13 Chemical stability of polynitroaliphatic compounds
- 1.13.1 Reactions with mineral acids
- 1.13.2 Reactions with base and nucleophiles
- References
- 2 Energetic Compounds 1: Polynitropolycycloalkanes
- 2.1 Caged structures as energetic materials
- 2.2 Cyclopropanes and spirocyclopropanes
- 2.3 Cyclobutanes and their derivatives
- 2.4 Cubanes
- 2.5 Homocubanes
- 2.6 Prismanes
- 2.7 Adamantanes
- 2.8 Polynitrobicycloalkanes
- 2.8.1 Norbornanes
- 2.8.2 Bicyclo[3.3.0]octane
- 2.8.3 Bicyclo[3.3.1]nonane
- References
- 3 Synthetic Routes to Nitrate Esters
- 3.1 Nitrate esters as explosives
- 3.2 Nitration of the parent alcohol
- 3.2.1O-Nitration with nitric acid and its mixtures
- 3.2.2O-Nitration with dinitrogen tetroxide
- 3.2.3O-Nitration with dinitrogen pentoxide
- 3.2.4O-Nitration with nitronium salts
- 3.2.5 Transfer nitration
- 3.2.6 OtherO-nitrating agents
- 3.3 Nucleophilic displacement with nitrate anion
- 3.3.1 Metathesis between alkyl halides and silver nitrate
- 3.3.2 Decomposition of nitratocarbonates
- 3.3.3 Displacement of sulfonate esters with nitrate anion
- 3.3.4 Displacement with mercury (I) nitrate
- 3.4 Nitrate esters from the ring-opening of strained oxygen heterocycles
- 3.4.1 Ring-opening nitration of epoxides
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- dinitrogen pentoxide 3.4.2 1,3-Dinitrate esters from the ring-opening nitration of oxetanes with
- 3.4.3 Other oxygen heterocycles
- 3.5 Nitrodesilylation
- 3.6 Additions to alkenes
- 3.6.1 Nitric acid and its mixtures
- 3.6.2 Nitrogen oxides
- 3.6.3 Metal salts
- 3.6.4 Halonitroxylation
- 3.7 Deamination
- 3.8 Miscellaneous methods
- 3.9 Synthetic routes to some polyols and their nitrate ester derivatives
- 3.10 Energetic nitrate esters
- References
- 4 Synthetic Routes to AromaticC-Nitro Compounds
- 4.1 Introduction
- 4.2 Polynitroarylenes as explosives
- 4.3 Nitration
- 4.3.1 Nitration with mixed acid
- 4.3.2 Substrate derived reactivity
- 4.3.3 Effect of nitrating agent and reaction conditions on product selectivity
- 4.3.4 Other nitrating agents
- 4.3.5 Side-reactions and by-products from nitration
- 4.4 Nitrosation–oxidation
- 4.5 Nitramine rearrangement
- 4.6 Reaction of diazonium salts with nitrite anion
- 4.7 Oxidation of arylamines, arylhydroxylamines and other derivatives
- 4.7.1 Oxidation of arylamines and their derivatives
- 4.7.2 Oxidation of arylhydroxylamines and their derivatives
- 4.8 Nucleophilic aromatic substitution
- 4.8.1 Displacement of halide
- 4.8.2 Nitro group displacement and the reactivity of polynitroarylenes
- 4.8.3 Displacement of other groups
- 4.8.4 Synthesis of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)
- 4.9 The chemistry of 2,4,6-trinitrotoluene (TNT)
- 4.10 Conjugation and thermally insensitive explosives
- References
- 5 Synthetic Routes toN-Nitro Functionality
- 5.1 Introduction
- 5.2 Nitramines, nitramides and nitrimines as explosives
- 5.3 Direct nitration of amines
- 5.3.1 Nitration under acidic conditions
- 5.3.2 Nitration with nonacidic reagents
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- 5.4 Nitration of chloramines viii Contents
- 5.4.1 Nitration of dialkylchloramines
- 5.4.2 Nitration of alkyldichloramines
- 5.5 N-Nitration of amides and related compounds
- 5.5.1 Nitration with acidic reagents
- 5.5.2 Nitration with nonacidic reagents
- 5.6 Nitrolysis
- 5.6.1 Nitrolysis of amides and their derivatives
- 5.6.2 Nitrolysis of N-alkyl bonds
- 5.6.3 Nitrolysis of nitrosamines
- 5.7 Nitrative cleavage of other nitrogen bonds
- 5.8 Ring-opening nitration of strained nitrogen heterocycles
- 5.8.1 Aziridines
- 5.8.2 Azetidines
- 5.9 Nitrosamine oxidation
- 5.10 Hydrolysis of nitramides and nitroureas
- 5.11 Dehydration of nitrate salts
- 5.12 Other methods
- 5.13 Primary nitramines as nucleophiles
- 5.13.1 1,4-Michael addition reactions
- 5.13.2 Mannich condensation reactions
- 5.13.3 Condensations with formaldehyde
- 5.13.4 Nucleophilic displacement reactions
- 5.14 Aromatic nitramines
- 5.15 The nitrolysis of hexamine
- 5.15.1 The synthesis of RDX
- 5.15.2 The synthesis of HMX
- 5.15.3 Effect of reaction conditions on the nitrolysis of hexamine
- 5.15.4 Other nitramine products from the nitrolysis of hexamine
- References
- 6 Energetic Compounds 2: Nitramines and Their Derivatives
- 6.1 Cyclopropanes
- 6.2 Cyclobutanes
- 6.3 Azetidines – 1,3,3-trinitroazetidine (TNAZ)
- 6.4 Cubane–based nitramines
- 6.5 Diazocines
- 6.6 Bicycles
- 6.7 Caged heterocycles – isowurtzitanes
- 6.8 Heterocyclic nitramines derived from Mannich reactions
- 6.9 Nitroureas
- 6.10 Other energetic nitramines
- 6.11 Energetic groups
- 6.11.1 Dinitramide anion
- 6.11.2 AlkylN,N-dinitramines
- 6.11.3N-Nitroimides
- References
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- 7 Energetic Compounds 3:N-Heterocycles Contents ix
- 7.1 Introduction
- 7.2 5-Membered rings – 1N – pyrroles
- 7.3 5-Membered rings – 2N
- 7.3.1 Pyrazoles
- 7.3.2 Imidazoles
- 7.3.3 1,3,4-Oxadiazoles
- 7.3.4 1,2,5-Oxadiazoles (furazans)
- 7.3.5 Benzofurazans
- 7.3.6 Furoxans
- 7.3.7 Benzofuroxans
- 7.4 5-Membered rings – 3N
- 7.4.1 Triazoles
- 7.4.2 Triazolones
- 7.4.3 Benzotriazoles
- 7.5 5-Membered rings – 4N
- 7.6 6-Membered rings – 1N – pyridines
- 7.7 6-Membered rings – 2N
- 7.8 6-Membered rings – 3N
- 7.9 6-Membered rings – 4N
- 7.10 Dibenzotetraazapentalenes
- References
- 8 Miscellaneous Explosive Compounds
- 8.1 Organic azides
- 8.1.1 Alkyl azides
- 8.1.2 Aromatic azides
- 8.2 Peroxides
- 8.3 Diazophenols
- 8.3.1 Diazophenols from the diazotization of aminophenols
- o-nitroarylnitramines 8.3.2 Diazophenols from the rearrangement of
- 8.4 Nitrogen-rich compounds from guanidine and its derivatives
- References
- 9 Dinitrogen Pentoxide – An Eco-Friendly Nitrating Agent
- 9.1 Introduction
- 9.2 Nitrations with dinitrogen pentoxide
- 9.3 The chemistry of dinitrogen pentoxide
- 9.4 Preparation of dinitrogen pentoxide
- 9.5 C-nitration
- 9.6 N-nitration
- 9.7 Nitrolysis
- 9.8 O-nitration
- 9.9 Ring cleavage nitration
