STUDIES OF LOW-TEMPERATURE OXIDATION REACTIONS.
Annual progress rept. no. 2, 1 Oct 63-30 Sep 64,
MONSANTO RESEARCH CORP DAYTON OHIO
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The autoxidation of trimethylborane has been investigated spectroscopically at 90-110K. The reactions of nitrosonium nitrate with some unsaturated hydrocarbons have been investigated at 77-195K. Ethylene, propene, and propyne were found to catalyze the isomerization of nitrosonium nitrate to a colorless isomeric species, presumably symmetrical dinitrogen tetroxide, in the presence of oxygen at 77-90K. Olefins that are more susceptible to electrophilic addition reactions undergo addition reactions. The reaction with isobutylene was investigated in detail by preparative vacuum line and by spectroscopic techniques. A very unstable solid, believed to be the cis-dimeric form of isobutylene nitrosonitrate, was isolated. 2-Nitratoisobutyraldoxime is the more readily isolatable product upon warm-up to room temperature. Symmetrical dinitrogen tetroxide dissolves in isobutylene at 195K. and remains unreactive. The role of nitrosonium nitrate in reactions of N2O4 with olefins is discussed. A verticalpath infrared cryocell, applicable for the study of reactions in solution at temperatures above 60K are described.