Abstract
The object of this work is to obtain a bettor understanding of the chemistry of the nitrolysis reaction of hexamine in nitric acid alone, this reaction giving primarily 3,5-dinitro-1,3,5-triasncyclohexane derivatives as final products. Aspects of the nitrolysis reactions of hexamine, some related quarternary derivatives, and 7-nitro-1,3, 5-triazaadamaniane in nitric acid and nitric acid/ammonium nitrate solution are investigated. The nitrosation, tosylation and mathylation reactions of 7-nitro-1,3,5-triazaadamantane are studied and found to be similar to those of hexamine. Preliminary variable temperature 1H NMR studies have been performed on the reactions of 1-methoxymothyl-3,5-dinitro-1,3,5-triazacyclohexane, 3,7-dinitro-1,3,5,7-tetraaaabicyclo(3.3.1)nonane and hexamine in nitric acid solution over the temperature range 243-303 K, in an attempt to follow the course of reaction and characterise the intermediates. In order to monitor these reactions the NMR characteristics of certain N-nitramines, N-nitrosamines, 1,3,5,7-tetraazabicyclo(3.3.1)nonaries, hexamine and derivatives are studied, for compounds from these classes may be expected to participate in the nitrolysis reactions. The nitrolysis reaction of 7-nitro-1,3,5-triazaadamantane gives either 1,3,7-triazabicyclo(3. 3. 1) nonane or 1,3,5-trinitro-1,3-diazacyclohexane derivatives as products. The nature of these products suggests that the mechanism of nitrolysis for this molecule occurs via a stepwise scission process. Due to similarities between the chemistry of hexamine and 7-nitro-1,3,5 -triazaadamantane, particularly with regards to the characteristics of the nitrolysis reaction, it is considered that the nitrolysis reaction of hexamine probably involves a similar mechanism. 1H, 13C, 14N NMR and INDO molecular orbital studies are performed on selected molecules from the classes of compounds considered in this work with a view to the elucidation of their electronic structures.