Based on a prior NMR study, a reinvestigation of the transamination reaction involving Me2AsNMe2 with secondary amines has identified the optimum reaction conditions that lead to high yields of the following acyclic [Me2AsNR2, where R = Et, Prn, Pr’*’, Bun, Bui, Ph, Bzl, and Cy] and cyclic [Me2AsR‘, where R’ = C4H4N-, C4H8N-, c5h15n-, c6h12n-,and CH3NC4H8N-] aminoarsines. These conditions are when Me2AsNMe2and the reacting amine are mixed neat in a 1:1 mole ratio. The highest yields are obtained with the less sterically demanding amines. Aminolysis and amination are found to be viable alternate synthetic pathways to Me2AsNCy2and Me2AsNPh2, respectively. These synthesis routes are compared and the synthesis of two new aminoarsines is reported. 13C and 1H NMR assignments for the synthesized aminoarsines were made and these data are compared with those of the parent amines. © 1991 by Marcel Dekker, Inc.