Nitroalkanes special

Nitro = ac/-nitro tautomerism occupies a special role as it has been speculated to occur under conditions where high energy explosives detonate. It has been proposed as one of the important initial steps responsible for the cascade of reactions leading to the high energy release during detonation [1], Nitro = aci-nitro tautomerism in nitro compounds RjCH-NO leads to nitronic acids, R2C=N(0)OH. Kinetic studies show similar pKa values for nitronic acids and their carbon counterparts, the carboxylic acids [1]. Nitroalkane = nitronic acid tautomerism has been assumed not to be an acid-catalyzed process because of the poor basicity of N02 group [4]. However, recent work by Erden et al. showed that this tautomerism can, in fact, be achieved under acid catalyzed... 

There is also the issue of the possible role of nitroalkanes as intermediate products, especially that small amoimts of them were found in the oxidation at low temperatures. Specially designed experiments with Ci—C3 nitroalkanes RNO2 showed that their decomposition in the system without O2 gives low concentration of oxygenates, primarily aldehydes, with the product composition dominated by carbon oxides and alkenes (for C2—C3 nitroalkanes). Addition of O2 increases the yield of carbon oxides and simultaneously decreases the yield of oxygenates. In addition, for the C2—C3 nitroalkanes, the selectivity of formation of alkenes is always higher than that of oxygenates. 

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