Nitramine compounds, neutral

Properties and reactions of nitramines Secondary nitramines are neutral, primary nitramines form salts with bases, but an excess of alkali often causes decomposition to the carbonyl compound, nitrogen, and water. Secondary nitramines and aqueous alkali afford nitrous acid, aldehyde, and primary amine. Acids decompose primary aliphatic nitramines with formation of nitrous oxide in a reaction that has not yet been clarified thus these compounds cannot be hydrolysed by acid to amines in the same way as nitrosamines, although, like the latter, they can be reduced to hydrazines. Primary and secondary aromatic nitramines readily rearrange to C-nitroarylamines in acid solution. Most nitramines decompose explosively when heated, but the lower aliphatic secondary nitramines can be distilled in a vacuum. 

This synthesis of N-nitromorpholine is representative of a rather general reaction for the preparation of both primary and secondary nitramines.3 It represents the simplest process for obtaining both types of compounds. The reaction is unique in that a nitration is carried out under neutral or alkaline conditions. Acetone cyanohydrin nitrate may also be used for the nitration of many active methylene compounds.8... 

This reaction can account for the high initial abundance of NO found when the initial HONO concentration is also high [30]. Third, some nitramines we have studied also contain aliphatic C-NO2 groups. C-NO2 compounds are found to generate a considerable amount of NO [39,40], perhaps because of the approximately thermally neutral C-NO2 to C-ONO isomerization [41]. CO-NO homolysis leading to NO is facile in this isomerized state. Fourth, there is evidence that nitramines can form nitrosamines (R2W-NO) upon thermal decomposition in the condensed phase [42-44]. Fast thermal decomposition of nitrosamines also liberates NO [45]. 

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