Selective Nitrations: The Laser-Induced Nitration of Three Cycloalkanes: II

The army uses nitrated compounds as explosives and propellants. There is a special need for propellants with the chemical composition necessary to burn exactly with high energy production, but with a minimum of side products which create smoke. Laser-induced chemistry possesses the potential to drive some reactions in an efficient and selective manner, and may be useful in driving nitration reactions toward specific products. Reported here are the results of several successful attempts to laser-induce the reactions of nitrogen oxides with three cycloalkanes. Specifically, the tunable, continuous wave, carbon dioxide infrared laser was used to drive the reaction between the nitrogen dioxide and cyclopropane, cyclobutane, and cyclopentane under a variety of reaction conditions. The spectrochemical analyses of the product mixtures are presented here. In addition to nitrocycloalkanes, other products resulting were either from ring cleavage, or from nitration or oxidation of ring fragments. By examining the effects of various reaction conditions on the product arrays, it was possible to find optimum conditions for producing the nitrocycloalkanes while minimizing side products.