Aristoff, E, Graham, JA, Meen, RH, Myers, GS & Wright, GF 1949, 'NITROLYSIS OF HEXAMETHYLENETETRAMINE: VI. RECOMBINATION OF FRAGMENTS DURING HEXAMETHYLENETETRAMINE NITROLYSIS IN ACETIC ANHYDRIDE', Canadian Journal of Research, vol. 27b, no. 6, pp. 520-544.
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Alternative hypotheses can account for the yield of more than one equivalent of Cyclonite from hexamine when the Bachmann reagents, ammonium nitrate, nitric acid, and acetic anhydride are used. In the nitrolysis, evidence for a stepwise synthesis from unit fragments is presented as the enhanced yield when methylenedinitramine is added with paraform to ammonium nitrate and acetic anhydride according to the Schiessler–Ross method for Cyclonite synthesis. However, this evidence is discounted because the expected by-product, 1,5-diacetoxy-2,4-dinitro-2,4-diazapentane is not found. Alternatively it is believed that the Bachmann reaction is actually a combination of the direct nitrolysis of hexamine with nitric acid, concurrent with a resynthesis of hexamine from the fragments produced by the nitrolysis. On this basis all by-products from the hexamethylenetetramine nitrolysis must be accounted as degradation products of hexamethylenetetramine and not capable of synthesis from unit fragments like formaldehyde, ammonia, and acetic acid. No exception has been found; the addition of acylamides to the Bachmann reaction mixture increases the yield of two by-products, 1-acyl-3,5-dinitro-1,3,5-triazacyclohexane and 1-acyl-3,5,7-trinitro-1,3,5,7-tetrazacycloöctane. It has been shown that these can be formed only from degradation products of hexamethylenetetramine such as 1,5-diaceto-3,7-endomethylene-1,3,5,7-tetrazacycloöctane and acetaminomethylhexamethylenetetramine nitrate.
Rice, SA 1949, 'William Lane Austin (1871–1949) James Clyde Capt (1888–1949)', Journal of the American Statistical Association, vol. 44, no. 248, pp. 565-566.
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Wright, GF & Myers, GS 1949, 'THE NITROLYSIS OF HEXAMETHYLENETETRAMINE: IV. SYNTHESIS OF A CYCLONITE HOMOLOGUE', Canadian Journal of Research, vol. 27b, no. 6, pp. 489-502.
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A homologue of Cyclonite has been prepared. This homologue, 1,3,6-trinitro-1,3,6-triazacycloheptane was formed by nitrolysis of methylene-bis-3,6-dinitro-1,3,6-triazacycloheptane, which was synthesized from N,N′-dimethylol-1,2-dinitraminoethane, formaldehyde, and ammonia. The reliability of this synthesis was established by analogous reactions. The nitrolysis yields also 1,8-diacetoxy-2,4,7-trinitro-2,4,7-triazaöctane via 1-acetoxymethyl-3,6-dinitro-1,3,6-triazacycloheptane. Ammonium nitrate has been shown to promote demethylolation in this series just as it does in the triazacyclohexane compounds. Analogies have therefore been drawn between these nitrolyses and that of hexamethylene-tetramine. Further comparisons derive from the isolation of 1-acetoxymethyl-3,6-dinitro-1,3,6-triazacycloheptane and 1-aceto-3,6-dinitro-1,3,6-triazacycloheptane by acetolysis of methylene-bis-dinitrotriazacycloheptane with acetic anhydride.
