N-chloro- and NN-dichloro-derivatives of some phosphinic amides preparation and reactions with anthracene, anisole, and triphenylarsine

Abstract

1-Amino-2,2,3,4,4-pentamethylphosphetan 1-oxide (5) and di-t-butylphosphinic amide (9) can be converted into the N-monochloro- and NN-dichloro-derivatives with t-butyl or sodium hypochlorite. The N-monochloroamides partially disproportionate in solution. They can be prepared conveniently by evaporation of the solvent from a solution containing equimolar amounts of the appropriate amide and NN-dichloroamide. The N-monochloroand NN-dichloro-derivatives of (5) are reduced to the amide by sodium methoxide in methanol; no rearrangement (ring-expansion) is observed. They react with anthracene to give 9-chloro- and 9,10-dichloro-anthracene and with anisole to give chloroanisole (mainly the para-isomer). Triphenylarsine reacts with the NN-dichloroamide to give (after reductive work-up) an arsoranylideneamine, which can also be prepared from the amide (5) and diacetoxytriphenylarsorane.