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Synthesis of Aromatic Polynitro Compounds Synthesis of Aromatic Polynitro Compounds By Joseph Michael Barry Christofi Submitted for the degree Doctor of Philosophy Christopher Ingold Laboratories August 1994 Department of Chemistry University College London ProQuest Number: 10018490 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest. ProQuest 10018490 Published by ProQuest LLC(2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. Microform Edition © ProQuest LLC. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 Abstract This thesis consists of two main areas of study: the first being the mixed acid nitration of compounds in the series where X = NH, S, SO, and SO2, and the second area of study being the mechanism of rearrangement of N-nitrocarbazole. For each compound in the above series, the aim was to synthesise polynitro derivatives in a pure state, with high yields for use as energy rich constituents of pyrotechnic compositions. The tetranitro compounds hold the most interest for this particular application. The first compound studied was carbazole (X = NH). 1-Nitro-, 3-nitro-, 1,6- dinitro-, and 3,6-dinitrocarbazole were synthesised by literature methods. The synthesis of 1,3,6, 8-tetranitrocarbazole, first achieved over forty years ago, was improved by changing it from a one step to a two step reaction. Nitration of dibenzothiophene (X = S) was hindered by the ease of oxidation of the sulphur atom. The 2-nitro-, 3-nitro-, 2,8-dinitro-, and 3,7-dinitrodibenzo- thiophenes were synthesised by literature methods. The 2,4,8-trinitro- and 2,4,6,8- tetranitrodibenzothiophenes were identified as minor constituents of product mixtures, after separation by preparative HPLC. Dibenzothiophene-5-oxide (X = SO) also proved difficult to nitrate further than the 3,7-dinitro- compound due to the ease of oxidation of the sulphoxide group. The 3-nitro- and 3,7-dinitro- compounds were synthesised by literature methods. The 2.8-dinitrodibenzothiophene-5-oxide was also synthesised. In dibenzothiophene-5,5-dioxide (X = SO2) there were no problems of further oxidation of the sulphone group during nitration. The 3-nitro, 2-nitro, and 3,7-dinitro­ compounds were synthesised by literature methods. The 2,7-dinitro-, 2,8-dinitro-, 1,3,7-trinitro- ,1,3, 8-trinitro- ,2,3,7-trinitro- ,2,3, 8-trinitro-, 1,3,7, 8-tetranitro-, and 2.3.7.8-tetranitro- compounds were also synthesised. The mechanism of the acid catalysed rearrangement of N-nitrocarbazole was studied using both and NMR spectroscopy. The rearrangement proved to be a difficult system to study. Small chemically induced dynamic nuclear polarisation (CIDNP) effects were observed in both the acid catalysed and the thermal rearrangements of N-nitrocarbazole. Dedicated to my parents Rita & Michael and my wife Jane without whose love, kindness, and understanding this would not have been possible Acknowledgements I would like to thank my supervisor at Royal Holloway and Bedford New College (RHBNC), Dr. J.P.B. Sandall, for all his help and encouragement throughout the first two years of my course, and my supervisor at University College London (UCL), Professor J.H. Ridd, for his help and encouragement throughout my final year and his enthusiastic assistance with my write up. I would also like to thank the technical staff at both colleges, especially Richard Williams at RHBNC, and Jill Maxwell, Steve Corker, and Alan Stones at UCL for all their help and analysis work. I would also like to thank Dr. D A. Tocher for the X-ray crystal determination. My thanks are extended to all my friends and fellow postgraduates at RHBNC and UCL, and special thanks to the other members of the Ridd group, Rob, Rupert and Stuart for their good humour throughout my final year, and their help with the NMR experiments. I would also like to thank my industrial supervisor Jim Queay, and the Procurement Executive, Ministry of Defence, for funding this work. I would like to thank my family and friends for their encouragement and support throughout my years at University. Finally I would like to thank my Mum, Dad, and my wife Jane for all their help, financial and emotional, and their endless encouragement and understanding. CONTENTS Title Page 1 Abstract 2 Dedication 4 Acknowledgements 5 Contents 6 Abbreviations 16 1. INTRODUCTION 1.1 Mixed Acid Nitration 17 1.1.1 Electrophilic aromatic nitration by the nitronium ion 17 1.1.2 Effect of nitrous acid 20 1.1.3 Olah’s modification of the Ingold mechanism 25 1.1.4 Schofield’s encounter pair 26 1.1.5 Electron transfer in nitration 27 1.1.6 Summary of the mechanism of electrophilic 28 aromatic nitration 1.1.7 Nitration of carbazole 29 1.1.8 Nitration of dibenzothiophene 30 1.1.9 Nitration of dibenzothiophene-5-oxide 32 1.1.10 Nitration of dibenzothiophene-5,5-dioxide 33 1.2 Chemically Induced Dynamic Nuclear Polarisation 34 (CIDNP) Effects 1.2.1 ^^N NMR spectroscopy 34 1.2.2 Interaction of an electron with an ^^N nucleus 36 1.2.3 Systems of two electrons 39 1.2.4 Conditions for CIDNP effects 40 1.2.5 Rearrangement of N-nitrocarbazole 43 2. RESULTS 2.1 N itrocarbazoles 49 2.1.1 3-Nitrocarbazole 49 2.1.2 1-Nitrocarbazole 53 2.1.3 1,6 -Dinitrocarbazole 56 2.1.4 3,6 -Dinitrocarbazole 59 2.1.5 1,3,6,8-T etranitrocarbazole 61 2.1.6 The tri-sodium salt of carbazole-1,3, 6 -trisulphonic acid 64 2.2 Rearrangement of N-nitrocarbazole 66 2.2.1 N-nitrosocarbazole 6 6 2.2.2 N-nitrocarbazole 69 2.2.3 Rearrangement of N-nitrocarbazole 71 2.2.3.1 Acid catalysed 71 2.2.3.2 Thermal 88 2.3 Nitrodibenzothiophenes 99 2.3.1 2-Nitrodibenzothiophene 99 2.3.2 2,8-Dinitrodibenzothiophene 103 2.3.3 3-Nitrodibenzothiophene 105 2.3.4 3,7-Dinitrodibenzothiophene 107 2.3.5 Low temperature nitration of 2, 8-dinitrodibenzothiophene 109 2.4 Nitrodibenzothiophene-5-oxides 115 2.4.1 Dibenzothiophene-5 -oxide 115 2.4.2 3-Nitrodibenzothiophene-5-oxide 117 2.4.3 3,7-Dinitrodibenzothiophene-5-oxide 119 2.5 Nitrodibenzothiophene-5.5 -dioxides 122 2.5.1 Dibenzothiophene-5,5-dioxide 122 2.5.2 3-Nitrodibenzothiophene-5,5-dioxide 124 2.5.3 3,7-Dinitrodibenzothiophene-5,5-dioxide 127 2.5.4 2-Nitrodibenzothiophene-5,5-dioxide 129 2.5.5 2,7-Dinitrodibenzothiophene-5,5-dioxide 132 2.5.6 2,8-Dinitrodibenzothiophene-5,5-dioxide 134 2.5.7 1,3,7-Trinitrodibenzothiophene-5,5-dioxide 137 2.5.8 1,3,8-Trinitrodibenzothiophene-5,5-dioxide 139 2.5.9 2,3,7-Trinitrodibenzothiophene-5,5-dioxide 142 2.5.10 2,3,8-Trinitrodibenzothiophene-5,5-dioxide 146 2.5.11 1,3,7,8-Tetranitrodibenzothiophene-5,5-dioxide 148 2.5.12 2,3,7, 8-Tetranitrodibenzothiophene-5,5-dioxide 150 3. DISCUSSION 3.1 N itrocarbazoles 153 3.2 Rearrangement of N-nitrocarbazole 157 3.3 Nitrodibenzothiophenes 161 3.4 Nitrodibenzothiophene-5-oxides 164 3.5 Nitrodibenzothiophene-5.5 -dioxides 164 4. CONCLUSIONS 4.1 Nitrocarbazoles 169 4.2 Rearrangement of N-nitrocarbazole 169 4.3 Nitrodibenzothiophenes 170 4.4 Nitrodibenzothionhene-5-oxides 171 4.5 N itrodibenzothiophene-5.5 -dioxides 171 5. APPARATUS AND REAGENTS 5.1 Analytical techniques 173 5.2 Reagents 174 6. EXPERIMENTAL 6.1 N itrocarbazoles 175 6.1.1 Synthesis of 3-nitrocarbazole 175 6.1.2 Synthesis of 1-nitrocarbazole 176 6.1.3 Synthesis of 1,6-and 3,6-dinitrocarbazole 177 6 .1.3.1 Synthesis of mixture of isomers 177 6 .1.3.2 Separation of isomers 177 6.1.4 Synthesis of 1,3, 6 ,8-tetranitrocarbazole 179 6 .1.4.1 Method from reference 53 179 6 .1.4.2 Method from reference 52 180 6.1.5 Synthesis of tri-sodium salt of carbazole-1,3, 6 -trisulphonic acid 181 6.1.6 Synthesis of 1,3,6, 8-tetranitrocarbazole in two stages 182 6.1.7 Large scale synthesis of 1,3,6, 8-tetranitrocarbazole 183 in two stages 6 .2 Rearrangement of N-nitrocarbazole 184 6.2.1 Synthesis of N-nitrosocarbazole 184 6.2.2 Synthesis of N-nitrocarbazole 184 6.2.3 Rearrangement of N-nitrocarbazole 185 6.2.3.1 Acid catalysed 185 6 .2.3.2 Thermal 186 6.3 N itrodibenzothiophenes 186 6.3.1 Synthesis of 2-nitrodibenzothiophene 186 6.3.2 Synthesis of 2, 8-dinitrodibenzothiophene 187 6.3.3 Synthesis of 3-nitrodibenzothiophene 188 6.3.4 Synthesis of 3,7-dinitrodibenzothiophene 189 6.3.5 Low temperature nitration of 2, 8-dinitrodibenzothiophene 189 6.4 Nitrodibenzothiophene-5-oxides 191 6.4.1 Synthesis of dibenzothiophene-5-oxide 191 6.4.2 Synthesis of 3-nitrodibenzothiophene-5-oxide 192 6.4.3 Synthesis of 3,7-dinitrodibenzothiophene-5-oxide 193 6.5 Nitrodibenzothiophene-5.5-dioxides 194 6.5.1 Synthesis of Dibenzothiophene-5,5-dioxide 194 6.5.2 Synthesis of 3-Nitrodibenzothiophene-5,5-dioxide 194 6.5.3 Synthesis of 3,7-Dinitrodibenzothiophene-5,5-dioxide 195 6.5 .3 .1 From Dibenzothiophene-5,5-dioxide 195 6 .5.3.2 From Dibenzothiophene 196 6.5.4 Synthesis of 2-Nitrodibenzothiophene-5,5-dioxide 196 6.5.5 Synthesis of 2,7-dinitrodibenzothiophene-5,5-dioxide 197 6.5.6 Synthesis of 2,8-dinitrodibenzothiophene-5,5-dioxide 198 6.5.7 Synthesis of 1,3,7-trinitrodibenzothiophene-5,5-dioxide 199 6.5.8 Synthesis of isomeric mixture of 1,3,8-, and 2,3,7-trinitro- 199 dibenzothiophene-5,5-dioxide 6.5.9 Synthesis of 2,3,8-trinitrodibenzothiophene-5,5-dioxide 200 6.5.10 Synthesis of 1,3,7,8-tetranitrodibenzothiophene-5,5-dioxide 201 6.5.11 Synthesis of 2,3,7,8-tetranitrodibenzothiophene-5,5-dioxide 202 7.
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