Nitroalkanes Polynitroalkanes

A review appeared on the determination of nitroalkanes, polynitroalkanes, nitroalkenes, aromatic nitro and polynitro compounds, heterocyclic nitro derivatives and inactive compounds after nitration, by polarography, voltammetry and HPLC with electrochemical detection441. 

Nitromethane is a detonable explosive, nitroethane can be detonated if both hot and under strong confinement, other nitroalkanes are mild oxidants under ordinary conditions, but precautions should be taken when they are subjected to high temperatures and pressures, since violent reactions may occur [1], Explosives are described consisting of nitromethane stabilised for transport by admixture with nitroethane or nitropropane, then resensitised by addition of an amine [4], The polynitroalkanes, being more in oxygen balance than the mono-derivatives, tend to explode more easily [2], and caution is urged, particularly during distillation [3], See also POLYNITROALKYL COMPOUNDS... 

The nitration of moderate to high molecular weight alkane substrates results in very complex product mixtures. Consequently, these reactions are only of industrial importance if the mixture of nitroalkane products is separable by distillation. Polynitroalkanes can be observed from the nitration of moderate to high molecular weight alkane substrates with nitrogen dioxide. The nitration of aliphatic hydrocarbons has been the subject of several reviews. 

Table 1.11 Reactions of nitroalkanes and polynitroalkanes with mineral acid ...

A number of papers deal with the N-NMR spectra of anions derived from mono- and polynitroalkanes. The change of structure from that of a true anion of aci-nitroalkane to that of a true nitrocarbanion was suggested in the series of anions of mono-, di-, and trinitroalkanes on the basis of the N spectra [SO]. Some data on the N, N, and resonance shifts were reported for nitroalkane anions [51—53] and O for nitroalkanes [54]. 

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