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.
View/Download from: Publisher's site
View description>>
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.
McKay, AF, Wright, GF, Chute, WJ, Downing, DC & Myers, GS 1949, 'THE NITROLYSIS OF HEXAMETHYLENETETRAMINE: I. THE SIGNIFICANCE OF 1,5-ENDOMETHYLENE-3,7-DINITRO-1,3,5,7-TETRAZACYCLOÖCTANE (DPT)', Canadian Journal of Research, vol. 27b, no. 4, pp. 218-237.
View/Download from: Publisher's site
View description>>
The nitrolysis of hexamethylenetetramine by the method of Hale yields, in addition to Cyclonite, an aqueous diluate which contains either dimethylolnitramide, its dinitrate ester, or both. The presence of dimethylolnitramide can be demonstrated by its condensation with methylenediamine to give 1,5-dinitro-3,7-endomethy¡ene-1,3,5,7-tetrazacycloöctane (DPT). The latter compound was identified by nitrolysis to 1,3,5,7-tetranitro-1,3,5,7-tetrazacycloöctane. The validity of the Mannich-type condensation of dimethylolnitramide from the Hale diluate (or from formaldehyde and nitramide) to form DPT has been attested by similar condensations with methylamine, ethylenediamine, cyclohexylamine, and benzylamine. In one of these condensations acetaldehyde has replaced part of the formaldehyde. Dimethylolnitramide has further been characterized by its conversion to 3,7-dinitro-3,7-diaza-1,5-dioxacycloöctane. Nitrolysis of the latter forms sym. dinitroxydimethylnitramide, which can be acetolyzed to sym. diacetoxydimethylnitramide.
MYERS, GS 1949, 'USAGE OF ANADROMOUS, CATADROMOUS AND ALLIED TERMS FOR MIGRATORY FISHES', COPEIA, no. 2, pp. 89-97.
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.
View/Download from: Publisher's site
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.
View/Download from: Publisher's site
View description>>
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.
