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

Article abstract of DOI:10.1246/bcsj.55.3312

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 deg 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.