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Durham E-Theses Durham E-Theses Mechanistic studies of the interactions of hexamine and some derivatives with electrophiles Scranage, John Keith How to cite: Scranage, John Keith (1989) Mechanistic studies of the interactions of hexamine and some derivatives with electrophiles, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/6562/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk 2 MECHANISTIC STUDIES OF THE INTERACTIONS OF HEXAMINE AND SOME DERIVATIVES WITH ELECTROPHILES by John Keith Scranage. Submitted for the degree of Doctor of Philosophy, 1989. ABSTRACT Mechanistic studies of the nitration of hexamethylene- tetramine (1.) and some derivatives are reported and are compared with acetylation reactions. Nitration reactions, with nitric acid, were carried out using mixtures of [^^N4]- and ^N4]-compounds, and the destination of the nitrogen isotopes in the products was determined mass spectro- metrically. The results show that in nitration of (1) to give 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT) extensive ring cleavage occurs to give species containing amino-nitrogen fragments. However, the nitration of 3,7-diacetyl-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DAPT) to 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]- nonane (DADN) involves selective cleavage of the methylene bridge. Kinetic studies are reported of the pH-dependence of the decomposition of DPT in aqueous media. The results show that at all acidities two stages are observed. The first stage, ki , involves catalysis by protons and hydroxide ions, and it is suggested that reaction occurs via a low concentration, ring-opened structure which is in equilibrium with DPT. In acidic solution an intermediate is observed which is identified as nitramide (NHoNOo). Methylenedinitroamine is shown not to be an intermediate in the decomposition of DPT, since its rate of decomposition is too slow. Mechanistic studies were also carried out on the synthesis and decomposition of 3,7-dinitroso-1,3,5,7- tetraazabicyclo [3.3.1]nonane (DNPT). Experiments using mixtures of [^^1^4]- and N4 ]-compounds showed that relatively little isotopic mixing occurs during nitrosation of (1) to DNPT, and hence the predominant reaction involves cleavage of a methylene bridge with the ring structure remaining intact. Data obtained for the decomposition of DNPT in acid solutions suggested that the rate-determining step of this process involves C-N bond cleavage, and were consistent with the intermediate formation of nitrosamine (NH2NO) . Kinetic studies were conducted on the decomposition of 3,7-bis(arylazo)-1,3,5,7-tetraazabicyclo[3.3.1]nonanes in acid solution to the corresponding aniline. Evidence was found for the formation of an intermediate methyleniminium ion, the UV/visible spectra of which could be observed in acetonitrile solutions containing only minute quantities of water. •''H NMR studies of solutions of hexamine in DMSO-dg containing electrophilic species suggested that under these conditions quaternary salts of hexaniine were formed, rather than cleavage of the molecule to form N-substituted six- and eight-membered ring species. The copyright of this thesis rests with the author. No quotation from it should be published without his prior written consent and information derived from it should be acknowledged. MECHANISTIC STUDIES OF THE INTERACTIONS OF HEXAMINE AND SOME DERIVATIVES WITH ELECTROPHILES by John Keith Scranage, B.Sc. Hons. (Dunelm) A thesis submitted for the degree of Doctor of Philosophy in the University of Durham, Department of Chemistry, 1989. - 2 NOV 1989 CONTENTS Page CHAPTER 1 Introduction 1 1.1: General properties of hexamine 2 1.2: Nitration of hexamine 5 1.3: Acetylation of hexamine 10 1.4: Nitrosation of hexamine 13 1.5: Reaction of diazonium ions with hexamine 15 1.6: Salt and complex formation 18 1.6.1 Salts with acids 18 - 1.6.2 Quaternary salt formation 20 1.6.3 Complex formation with phenols 23 1.6.4 Complex formation with inorganic salts 23 1.7: Reactions with halogens and inorganic halides 24 1.8: References 26 CHAPTER 2: Experimental 31 2.1: Materials 32 2.1.1: Solvents 32 2.1.2: Gases 33 2.1.3: Salts 33 2.1.4: Substrates 35 2.1.5: Buffer solutions 42 2.2: Measurement techniques 42 2.2.1: UV/Visible measurements 42 2.2.2: Mass spectrometry 45 46 2.2.3: NMR spectrometry 46 2.2.4: pH measurements - i - Page 2.2.5 Quantitative determination of formaldehyde 46 2.3; Attempted preparation of DADN by acetylation of DPT 47 2.4: References 50 CHAPTER 3; Mechanistic studies of the formation of DPT and DADN using ^^N-compounds 51 3.1: Introduction 52 3.2: Experimental 53 " 3.3: Investigation of the mechanism of formation of DPT via nitration of hexgunine 55 3.4; Investigation of the mechanism of formation of DADN via nitration of DAPT 60 3.5: The selective cleavage of 1,3,5,7- tetraazabicyclo[3.3.l]nonanes 62 3.6: Discussion 64 3.7: References 67 CHAPTER 4; The decomposition of DPT in acidic and basic aqueous solutions 68 4.1: Introduction 69 4.2: UV spectra of DPT 69 4.3: Kinetic data for the decomposition of DPT 72 4.4: The role of methylenedinitroamine 76 11 Page 4.4.1: The decomposition of MDNA in aqueous solution 79 80 4.4.2: UV spectra of MDNA 4.4.3: Quantitative determination of formaldehyde liberation during the decomposition of MDNA 83 4.4.4: Determination of a pH profile for the decomposition of MDNA 83 4.4.5: Determination of the pK„ values of MDNA 91 a 94 4.5: The role of nitramide 4.5.1: UV spectra of nitramide 94 4.5.2: Kinetic analysis of the decomposition of nitramide in aqueous solution 96 4.6: Discussion 101 4.7: References 107 CHAPTER 5 Studies on dinitrosopentamethylene- tetramine 109 5.1 Introduction 110 5.2 Mechanistic studies using ^^N-compounds 111 5.3 The decomposition of DNPT in aqueous solutions 114 5.3.1 Determination of formaldehyde liberated during the decomposition of DNPT in acid media 119 5.4 References 121 111 Page CHAPTER 6 Studies on the decomposition of 3,7- bis(arylazo)-1,3,5,7-tetraazabicyclo- 'S. 3.1] nonanes in acid solution 122 6.1: Introduction 123 6.2: UV spectra of bis(arylazo) compounds 123 6.3: Kinetic data for the decomposition of 3,7-bis(p-ethoxycarbonylphenylazo)- 1,3,5,7-tetraazabicyclo[3.3.1] nonane in acid solution 126 6.4: The role of triazenes 150 6.4.1 UV spectra of 1-(p-ethoxycarbonylphenyl)- 3-methyltriazene 153 6.4.2; Kinetic data for the decomposition of 1- (p- ethoxycarbonylphenyl)- 3-methyl- triazene in acid solution 154 6.5; Discussion 157 6.6; References 160 CHAPTER 7; "'"H NMR studies on the interaction of electrophiles with hexamine 162 7.1: Introduction 163 7.2: Interaction of hexamine with nitronium ion 164 7.3: Interaction of hexamine with nitrosonium ion 169 7.4: Interaction of hexamine with fuming nitric acid 172 - IV - Page 7.5: Interaction of hexamine with dinitrogen pentoxide 175 7.6: Interaction of hexamine with acetyl chloride 178 7.7: Interaction of DAPT with acetyl chloride 183 7.8: References 187 APPENDIX I: Research colloquia, seminars, lectures and conferences 188 (A) : Research colloquia, seminars and lectures organised by Durham University Chemistry Department, 1986-1989 190 (B) : Lectures organised by Durham University Chemical Society, 1986-1989 194 (C) : Conferences attended 197 (D) : First year induction course 197 - V ACKNOWLEDGEMENTS I would like to thank ray supervisor, Dr. M.R. Crampton, for his help and encouragement during this work. I would also like to thank other members of the department who helped in any way, particularly Mr. C. Greenhalgh for technical assistance, Dr. M. Jones for mass spectra, Dr. R. Matthews for NMR spectra, and Dr. A. Royston for acting as computer consultant. Thanks are also due to my industrial supervisor. Dr. P. Golding of R.A.R.D.E., Valtham Abbey, for advice on synthetic methods, and to the the Procurement Executive, Ministry of Defence for funding the project. - VI - PUBLICATIONS Some of the work in this thesis has been the subject of the following papers: '^^N Studies of the Mechanisms of Nitration of Hexamethylenetetramine and 3,7-Diacetyl-1,3,5,7- tetraazabicyclo[3.3.l]nonane', Tetrahedron, 1988, 44? 1679. 'Kinetic Studies of the pH Dependence of the Decomposition of 3,7-Dinitro-l,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT) and Related Compounds', J.Chem.Soc. Perkin Trans.II, 1989, 77. 'Mechanistic Studies on the Synthesis and Decomposition of 3,7-Dinitroso-1,3,5,7-tetraazabicyclo[3.3.1]nonane', J.Chem.Res. (S), 1989, 72. Vll DECLARATION The material in this thesis is the result of research carried out in the Department of Chemistry, University of Durham, between October 1986 and October 1989.
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