Photochemical reactions of substituted benzenes with aliphatic amines

Abstract

The products arising from the irradiation of diethylamine and t-butylamine with toluene, chlorobenzene, anisole, benzonitrile, benzyl fluoride, benzotrifluoride (α,α,α-trifluorotoluene),m-fluorobenzotrifluoride (α,α,α,m-tetrafluorotoluene), p-fluorotoluene, m-fluorotoluene, p-fluoroanisole, m-fluoroanisole, and 1,3-bis (trifluoromethyl) benzene, and of triethylamine with toluene, benzotrifluoride and 1,3-bis (trifluoromethyl) benzene, all at 254 nm, are described. Reaction pathways involving both substitution and 1,2-and 1,4-acyclic addition processes are observed and which predominates depends upon the arene substituent. The novel acyclic adduct, Me₂ CCH–CHCH–CHNBu^t, is obtained from toluene and t-butylamine and, contrary to previous reports, chlorobenzene yields arene-amine 1 : 1 adducts as well as the amine α-substitution product (16); benzonitrile gives aniline derivatives with the primary and secondary amines.