The Reactions of Singlet NH Radicals with Methyl and Ethyl Alcohols in the Liquid Phase

The reactions of the singlet NH(a1Δ) radicals with alcohols were studied by the photolyses of hydrogen azide in liquid methyl and ethyl alcohols at the temperature of Dry Ice–methyl alcohol and at 0 °C. The main products were nitrogen, ammonia, and oxime ethers; acetaldehyde oxime O-ethyl ether from ethyl alcohol and formaldehyde oxime O-methyl ether from methyl alcohol. The relative yields of the products were independent of the changes in the reaction temperature and in the concentration of the hydrogen azide examined. Methoxyamine or ethoxyamine, a possible insertion product of the singlet NH into the O–H bond of alcohol, was detected as a form of oxime ether by the reactions with the aldehyde eventually formed. It was concluded that the singlet NH radicals can effectively insert into the O–H bond of the alcohol.