JWBK121-FM October 11, 2006 21:10 Char Count= 0 Organic Chemistry of Explosives Dr. Jai Prakash Agrawal CChem FRSC (UK) Former Director of Materials Defence R&D Organisation DRDO House, New Delhi, India email: [email protected] Dr. Robert Dale Hodgson Consultant Organic Chemist, Syntech Chemical Consultancy, Morecambe, Lancashire, UK Website: http://www.syntechconsultancy.co.uk email: [email protected] iii JWBK121-FM October 11, 2006 21:10 Char Count= 0 iii JWBK121-FM October 11, 2006 21:10 Char Count= 0 Organic Chemistry of Explosives i JWBK121-FM October 11, 2006 21:10 Char Count= 0 ii JWBK121-FM October 11, 2006 21:10 Char Count= 0 Organic Chemistry of Explosives Dr. Jai Prakash Agrawal CChem FRSC (UK) Former Director of Materials Defence R&D Organisation DRDO House, New Delhi, India email: [email protected] Dr. Robert Dale Hodgson Consultant Organic Chemist, Syntech Chemical Consultancy, Morecambe, Lancashire, UK Website: http://www.syntechconsultancy.co.uk email: [email protected] iii JWBK121-FM October 11, 2006 21:10 Char Count= 0 Copyright C 2007 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England Telephone (+44) 1243 779777 Email (for orders and customer service enquiries): [email protected] Visit our Home Page on www.wiley.com All Rights Reserved. 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ISBN-13: 978-0-470-02967-1 (cloth : alk. paper) ISBN-10: 0-470-02967-6 (cloth : alk. paper) 1. Explosives. I. Hodgson, R. D. II. Title. TP270.A36 2006 662.201547—dc22 2006022827 British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN-13 978-0-470-02967-1 (HB) ISBN-10 0-470-02967-6 (HB) Typeset in 10/12pt Times by TechBooks, New Delhi, India Printed and bound in Great Britain by Antony Rowe Ltd, Chippenham, Wiltshire This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees are planted for each one used for paper production. iv JWBK121-FM October 11, 2006 21:10 Char Count= 0 Contents Foreword page xi Preface xiii Abbreviations xv Acknowledgements xxiii Background xxv 1 Synthetic Routes to Aliphatic C-Nitro Functionality 1 1.1 Introduction 1 1.2 Aliphatic C-nitro compounds as explosives 2 1.3 Direct nitration of alkanes 2 1.4 Addition of nitric acid, nitrogen oxides and related compounds to unsaturated bonds 3 1.4.1 Nitric acid and its mixtures 3 1.4.2 Nitrogen dioxide 4 1.4.3 Dinitrogen pentoxide 5 1.4.4 Nitrous oxide and dinitrogen trioxide 6 1.4.5 Other nitrating agents 6 1.5 Halide displacement 7 1.5.1 Victor Meyer reaction 7 1.5.2 Modified Victor Meyer reaction 9 1.5.3 Ter Meer reaction 10 1.5.4 Displacements using nitronate salts as nucleophiles 13 1.6 Oxidation and nitration of C–N bonds 14 1.6.1 Oxidation and nitration of oximes 14 1.6.2 Oxidation of amines 19 1.6.3 Nitration of nitronate salts 21 1.6.4 Oxidation of pseudonitroles 23 1.6.5 Oxidation of isocyanates 23 1.6.6 Oxidation of nitrosoalkanes 24 1.7 Kaplan–Shechter reaction 24 1.8 Nitration of compounds containing acidic hydrogen 27 1.8.1 Alkaline nitration 27 1.8.2 Acidic nitration 31 1.9 Oxidative dimerization 32 v JWBK121-FM October 11, 2006 21:10 Char Count= 0 vi Contents 1.10 Addition and condensation reactions 33 1.10.1 1,2-Addition reactions 33 1.10.2 1,4-Addition reactions 35 1.10.3 Mannich reaction 43 1.10.4 Henry reaction 44 1.11 Derivatives of polynitroaliphatic alcohols 46 1.12 Miscellaneous 49 1.12.1 1,1-Diamino-2,2-dinitroethylenes 49 1.12.2 Other routes to aliphatic nitro compounds 50 1.12.3 Selective reductions 51 1.13 Chemical stability of polynitroaliphatic compounds 51 1.13.1 Reactions with mineral acids 52 1.13.2 Reactions with base and nucleophiles 52 References 55 2 Energetic Compounds 1: Polynitropolycycloalkanes 67 2.1 Caged structures as energetic materials 67 2.2 Cyclopropanes and spirocyclopropanes 68 2.3 Cyclobutanes and their derivatives 69 2.4 Cubanes 71 2.5 Homocubanes 74 2.6 Prismanes 78 2.7 Adamantanes 79 2.8 Polynitrobicycloalkanes 82 2.8.1 Norbornanes 82 2.8.2 Bicyclo[3.3.0]octane 84 2.8.3 Bicyclo[3.3.1]nonane 85 References 85 3 Synthetic Routes to Nitrate Esters 87 3.1 Nitrate esters as explosives 87 3.2 Nitration of the parent alcohol 90 3.2.1 O-Nitration with nitric acid and its mixtures 90 3.2.2 O-Nitration with dinitrogen tetroxide 93 3.2.3 O-Nitration with dinitrogen pentoxide 93 3.2.4 O-Nitration with nitronium salts 94 3.2.5 Transfer nitration 95 3.2.6 Other O-nitrating agents 96 3.3 Nucleophilic displacement with nitrate anion 97 3.3.1 Metathesis between alkyl halides and silver nitrate 97 3.3.2 Decomposition of nitratocarbonates 98 3.3.3 Displacement of sulfonate esters with nitrate anion 98 3.3.4 Displacement with mercury (I) nitrate 99 3.4 Nitrate esters from the ring-opening of strained oxygen heterocycles 99 3.4.1 Ring-opening nitration of epoxides 99 JWBK121-FM October 11, 2006 21:10 Char Count= 0 Contents vii 3.4.2 1,3-Dinitrate esters from the ring-opening nitration of oxetanes with dinitrogen pentoxide 102 3.4.3 Other oxygen heterocycles 103 3.5 Nitrodesilylation 103 3.6 Additions to alkenes 104 3.6.1 Nitric acid and its mixtures 104 3.6.2 Nitrogen oxides 105 3.6.3 Metal salts 106 3.6.4 Halonitroxylation 106 3.7 Deamination 106 3.8 Miscellaneous methods 107 3.9 Synthetic routes to some polyols and their nitrate ester derivatives 108 3.10 Energetic nitrate esters 112 References 117 4 Synthetic Routes to Aromatic C-Nitro Compounds 125 4.1 Introduction 125 4.2 Polynitroarylenes as explosives 126 4.3 Nitration 128 4.3.1 Nitration with mixed acid 129 4.3.2 Substrate derived reactivity 131 4.3.3 Effect of nitrating agent and reaction conditions on product selectivity 138 4.3.4 Other nitrating agents 139 4.3.5 Side-reactions and by-products from nitration 143 4.4 Nitrosation–oxidation 144 4.5 Nitramine rearrangement 145 4.6 Reaction