Direct Amination of Benzene with Ammonia by Flow Plasma Chemistry.

Amine derivatives, including aniline and allylic amines, can be formed in a single-step process from benzene and an ammonia plasma in a microreactor. Different process parameters such as temperature, residence time, and plasma power were evaluated to improve the reaction yield and its selectivity toward aminated products and avoid hydrogenated or oligomerized products. In parallel, simulation studies of the process have been carried out to propose a global mechanism and gain a better understanding of the influence of the different process parameters. The exploration of diverse related alkenes showed that the double bonds, conjugation, and aromatization influenced the amination mechanism. Benzene was the best reactant for amination based on the lifetime of radical intermediates. Under optimized conditions, benzene was aminated in the absence of catalyst with a yield of 3.8 % and a selectivity of 49 % in various amino compounds.