Organic Chemistry of Explosives

ISBN-13: 9780470029671 / Angielski / Twarda / 2007 / 416 str.

Jai Prakash Agrawal; Robert Dale Hodgson

Opis

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.

Recenzje

"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)

Spis treści

Foreword.

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.

O autorze

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.

Blurb

Explosives have attracted some unwanted publicity over the years for their misuse in the taking of life and the destruction of property. Although such concerns and views are not unfounded, there is a bigger picture. More explosives have been used in times of peace than in all of the wars and conflicts put together. How many of the great engineering achievements would have been possible if not for the intervention of explosives? Explosives are in fact no more than tools and remain as some of the most fascinating products of chemistry.

 Organic Chemistry of Explosives is the first text which brings together in one volume the essential methods and routes used for the synthesis of organic explosives. Topics are organised based on the fact that explosive properties are imparted into a compound by the presence of certain functional groups, and include: 

• the methods which can be used to introduce C–nitro, O–nitro, and N–nitro functionality into organic compounds
• the synthesis of energetic compounds in the form of polynitropolycycloalkanes, caged and strained nitramines, and N–heterocycles
• the synthesis of explosives containing functionality less widely encountered, including: organic azides, peroxides, diazophenols, and energetic compounds derived from guanidine and its derivatives
• nitration with dinitrogen pentoxide and its likely significance for the future synthesis of energetic materials.    

 This book also highlights important properties such as melting points, impact sensitivities and velocities of detonation etc. which are considered valuable from the end–use point of view.

 Organic Chemistry of Explosives is an essential reference source for chemists working in the field of energetic materials and all those with an interest in the chemistry of nitramines, nitro compounds, nitrate esters, and nitration in general.