Formation of amines from aromatic hydrocarbons and molecular nitrogen during the reducing fixation of N2

Abstract

We have found that the fo rmat ion of amines during the reducing fixation of ni t rogen can in a numb er of c a se s a lso occur d i rec t ly f r o m the a rom a t i c hydroca rbons . Thus N 2 r eac t s at 20~ with a mix ture of naphthalene and excess meta l l i c l i thium in t e t r ahydro fu ran to fo rm (after hydro lys i s of the reac t ion mixture) ammonia and smal l amounts of c_,-naphthylamine.* S imi la r ly , in the reac t ion of ni t rogen with l i thium and diphenyl, ammonia and a mix tu re of o and p-aminodiphenyls a re obtained. In the absence of naphthalene (or diphenyl) }42 undergoes a lmos t no reac t ion with Li under these conditions. The yie lds of amines and a m monia depend on the concent ra t ion of the a ro ma t i c hydroca rbon and on the mo la r ra t io of Li to hydrocarbon . F o r Li:naphthalene = 16:1, the yield of c~-naphthylamine is 0.2-0.3% based on naphthalene (naphthalene concent ra t ion 0.8 M, N 2 p r e s s u r e 100 arm).