Formaldehyde primary nitramines

The products obtained from these condensations are predictable for simple mono-functional substrates primary amines usually form compounds where two equivalents of primary nitramine are incorporated into the product (Equation 5.19), whereas simple secondary amines can only combine with one equivalent of nitramine (Equation 5.20). The bis-nitramine (185) is formed from the reaction of methylamine with two mole equivalents each of methyl-nitramine and formaldehyde. 

The use of primary nitramines in Mannich reactions is an important route to numerous secondary nitramines. However, a far more common route to such nitramines involves the Mannich condensation of a terminal gem-dinitroalkane, formaldehyde, and an amine, followed by IV-nitration of the resulting polynitroalkylamine. The preformed methylol derivative of the gem-dinitroalkane is often used in these reactions and so formaldehyde can be omitted. This route has been used to synthesize explosives like (92) and (209). ... 

The condensation of a primary nitramine with formaldehyde in the presence of concentrated sulfuric acid is a useful route to 1,3-dinitramines. A number of linear dinitramines have been prepared via this route including 2,4-dinitro-2,4-diazapentane (212), 3,5-dinitro-3,5-diazaheptane (213), and 5,7-dinitro-5,7-diazaundecane (214). ... 

Under aqueous conditions formaldehyde reacts with primary nitramines to form the corresponding methylol derivatives. The versatility of the terminal hydroxy group of these methylol derivatives is illustrated by their facile conversion to more reactive functional groups, like isocyanates, which can then be reacted with compounds containing hydroxy or carboxy functionality. Diisocyanates like (215), (216) and (217) have been reacted with various polyni-troaliphatic diols for the synthesis of energetic polymers. ... 

As early as 1910, Franchimont[16] observed that primary nitramines (and nitro-paraffins) react with formaldehyde and secondary amines (e.g. piperidine). The formation of aminomethylnitramines (IV) then occurs ... 

Mannich condensations involving polyamines or polynitramines are more complex, and in the case of linear dinitramines, leads to very interesting and diverse chemistry, enabling the synthesis of many cyclic nitramine products. The reaction of methylenedinitramine (168) with various primary amines in the presence of formaldehyde leads to l,5-dinitro-l,3,5,7-tetraazacyclooctanes the 3,7-dimethyl analogue (186) is isolated when methylamine is used. ... 

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