Photoinduced Nucleophilic Addition of Ammonia and Alkylamines to Aryl-Substituted Alkenes in the Presence of <i>p</i>-Dicyanobenzene

Abstract

Abstract The photoamination of 1,1-diphenylpropene (1a) with ammonia and some primary alkylamines in the presence of p-dicyanobenzene gave the corresponding N-substituted 2-amino-1,1-diphenylpropane (2a–e) along with the formation of 3-methyl-4,4-diphenylbutanenitrile (3a), 1,1-diphenylpropane (4a), 3,3-diphenylpropene (5), and diphenylmethane (6). In the case of 1,1-diphenylethene (1b), N-substituted 1-amino-2,2-diphenylethane (2f–h), 4,4-diphenylbutanenitrile (3b), and 1,1-diphenylethane (4b) were produced. In photoamination with t-butylamine in acetonitrile, 3a and 3b were mainly formed as a consequence of the incorporation of acetonitrile to 1a and 1b. The photoamination of 1-phenyl-3,4-dihydronaphthalene (1c) with isopropylamine or t-butylamine gave cis- and trans-N-substituted 1-phenyl-2-amino-1,2,3,4-tetrahydronaphthalenes (15 and 16) in a ratio of ca. 8:2. The mechanism of photoamination is discussed in terms of a photochemical electron transfer of 1 to p-dicyanobenzene followed by a nucleophilic addition of the amine to the cation radical of 1.