Mechanistic studies in the synthesis of substituted nitrotriazacyclohexanes and related systems

• Main Author: Roberts, John Christopher
• Published: Royal Holloway, University of London 1971
• Subjects: 547; Organic Chemistry
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.704153

A survey of the literature relevant to the general chemistry of cyclic nitramines is reported with special reference to the formation of RDX from the nitration of hexamethylenetetramine. The various intermediates in the reaction sequence which have been suggested are reported. Part of the work reported in this thesis has been concerned with the isolation of one of the proposed intermediates in this reaction, and in this connection model systeme of piperidine and succinimide have been synthesised and investigated in order to compare their reactivity. The reaction between 1-Chloromethyl-3,5-dinitro-3,5-triazacyclohexane and silver nitrate has been investigated in some detail and the products of the reaction isolated and their structure determined. A mechanism for this reaction is proposed which involves the intermediacy of a nitrate ester. The nitrosation of alkoxymethyl derivatives of 3,5-dinitro-1,3,5-triazacyclohexane by dinitrogen tetroxide has been investigated and shown to produce, in excellent yields, the corresponding nitrosauiinc. A kinetic study has been carried out into this reaction and the results indicate a reaction which shows a first order dependence on both the substrate and molecular dinitrogen tetroxide. The second order rate constant has been determined at 20 and 30. A mechanism is suggested to account for these observations. Finally, an account of the use of mass spectrometryin observing these systems is reported. Fragmentation patterns have been determined and the results indicate a high degree of rearrangement at the temperatures required for mass spectral measurements. Nuclear magnetic resonance spectra of importance are reported and the likely conformation of the molecule DPT suggested by interpretation of its spectrum.