Other routes to aliphatic nitro compounds

A number of routes to aliphatic nitro compounds are not used for energetic materials synthesis but are included here for completeness. 

Bachmann and Biermann reported the synthesis of nitroalkanes from the thermolysis of acyl nitrates. The thermolysis of nitrite and nitrate esters over an asbestos catalyst is also reported to yield nitroalkanes.  

Olah and co-workers reported the synthesis of nitroalkanes and nitroalkenes from the nitrodesilylation of alkylsilanes and allylsilanes, respectively, with nitronium salts. 

Nitroacetylenes are generally unstable and very explosive and so they have been little studied. Schmitt and co-workers used the nitrodesilylation of trialkylsilylacetylenes with both nitronium salts and nitryl fluoride to obtain nitroacetylenes. Dinitrogen pentoxide has also been used for the nitrodesilylation of trialkylsilylacetylenes. Nitrodestannylation of allylsilanes has also been reported.  

Diels-Alder reactions using highly reactive polynitroalkenes have been reported. These include cycloaddition reactions with 1,1-dinitroethene, 1,1,2,2-tetranitroethylene and various fluoro-1,2-dinitroethylenes.  

---