REACTION OF NITROSONIUM NITRATE WITH ISOBUTYLENE AT 77-195 DEGREES K

The reactivity of nitrosonium nitrate toward some unsaturated compounds was investigated in the 77-195°K temperature range. Ethylene, propene, and propyne did not undergo addition reactions, whereas the products obtained from 1,3-butadiene and isoprene were very unstable upon warm-up. The experimentally most amenable system, consisting of isobutylene and nitrosonium nitrate in ethane-propane solution, was studied most extensively. The reactions were conducted at temperatures at which the symmetrical form of N2O4 is unreactive toward isobutylene. An unstable solid, believed to be the cis dimeric form of isobutylene nitrosonitrate, was isolated. This solid was converted into a thermally unstable liquid product at temperatures above 0°. The chemical and physical characteristics of the latter are consistent with 2-nitratoisobutyraldoxime structure. The role of nitrosonium nitrate in the reactions of N2O4 with olefins is discussed.