Organic Chemistry of Explosives

Preface.

Abbreviations.

Acknowledgements.

Background.

1 Synthetic Routes to Aliphatic C-Nitro Functionality.

1.1 Introduction.

1.2 Aliphatic C-nitro compounds as explosives.

1.3 Direct nitration of alkanes.

1.4 Addition of nitric acid, nitrogen oxides and related compounds to unsaturated bonds.

1.5 Halide displacement.

1.6 Oxidation and nitration of C–N bonds.

1.7 Kaplan–Shechter reaction.

1.8 Nitration of compounds containing acidic hydrogen.

1.9 Oxidative dimerization.

1.10 Addition and condensation reactions.

1.11 Derivatives of polynitroaliphatic alcohols.

1.12 Miscellaneous.

1.13 Chemical stability of polynitroaliphatic compounds.

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.

3 Synthetic Routes to Nitrate Esters.

3.1 Nitrate esters as explosives.

3.2 Nitration of the parent alcohol.

3.3 Nucleophilic displacement with nitrate anion.

3.4 Nitrate esters from the ring-opening of strained oxygen heterocycles.

3.5 Nitrodesilylation.

3.6 Additions to alkenes.

3.7 Deamination.

3.8 Miscellaneous methods.

3.9 Synthetic routes to some polyols and their nitrate ester derivatives.

3.10 Energetic nitrate esters.

4 Synthetic Routes to Aromatic C-Nitro Compounds.

4.1 Introduction.

4.2 Polynitroarylenes as explosives.

4.3 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.

4.8 Nucleophilic aromatic substitution.

4.9 The chemistry of 2,4,6-trinitrotoluene (TNT).

4.10 Conjugation and thermally insensitive explosives.

References.

5 Synthetic Routes to N-Nitro Functionality.

5.1 Introduction.

5.2 Nitramines, nitramides and nitrimines as explosives.

5.3 Direct nitration of amines.

5.4 Nitration of chloramines.

5.5 N-Nitration of amides and related compounds.

5.6 Nitrolysis.

5.7 Nitrative cleavage of other nitrogen bonds.

5.8 Ring-opening nitration of strained nitrogen heterocycles.

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.

5.14 Aromatic nitramines.

5.15 The nitrolysis of hexamine.

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 271

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.

7 Energetic Compounds 3: N-Heterocycles.

7.1 Introduction.

7.2 5-Membered rings - 1N - pyrroles.

7.3 5-Membered rings – 2N.

7.4 5-Membered rings – 3N.

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.

8 Miscellaneous Explosive Compounds.

8.1 Organic azides.

8.2 Peroxides.

8.3 Diazophenols.

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.

9.10 Selective O-nitration.

9.11 Synthesis of the high performance and eco-friendly oxidizer – ammonium dinitramide.

References.

Index.