The Reactions of Singlet NH Radicals with C4 Olefins in the Liquid Phase

Article abstract of DOI:10.1246/bcsj.56.662

The reactions of NH radicals with C4 olefins, trans- and cis-2-butenes, 1-butene, and isobutene, were investigated by the photolysis of hydrogen azide in the liquid olefin at 0 deg C and at the temperature of Dry Ice-methanol.Except for nitrogen and ammonia, amines and aziridines were found to be formed in good yield. 2-Butene-1-amine and trans-2,3-dimethylaziridine from trans-2-butene, 2-butene-1-amine and cis-2,3-dimethylaziridine from cis-2-butene, 3-butene-1- and 2-amines and 2-ethylaziridine from 1-butene, and 2-methyl-2-propene-1-amine and 2,2-dimethylaziridine from isobutene.These product formations were successfully explained by the insertion into the C-H bond and the addition to the double bond of olefin by the singlet NH radicals.In the case of 2-butene, no isomerized aziridine formation was observed.This result suggested that the triplet NH radicals rarely add to the double bond of olefin.