STUDIES OF LOW-TEMPERATURE OXIDATION REACTIONS.

Abstract

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.

Document Details

Document Type
Technical Report
Publication Date
Jan 08, 1965
Accession Number
AD0609800

Entities

People

  • H. R. Dufour
  • J. T. Miller Jr.
  • L. Parts

Organizations

  • Monsanto

Tags

DTIC Thesaurus Topics

  • Acyclic Hydrocarbons
  • Addition Reactions
  • Alkenes
  • Ethylenes
  • Hydrocarbons
  • Low Temperature
  • Nitrogen Oxides
  • Oxidation
  • Oxygen
  • Tetroxides
  • Unsaturated Hydrocarbons

Fields of Study

  • Chemistry

Readers

  • Organic Chemistry