N-(DIPHENYLPHOSPHINOTHIOYL)HYDROXYLAMINE - PREPARATION, CHARACTERIZATION AND BASE-INDUCED TRANSPOSITION OF SULFUR AND OXYGEN-ATOMS IN ITS O-BENZOYL DERIVATIVE

N-(Diphenylphosphinothioyl)hydroxylamine 5 has been prepared from Ph2P (S)Cl using H2NOSiMe3 and has been converted into its O-benzoyl deriva tive Ph2P(S)NHOCOPh 6. The principal reaction of the derivative 6 with base (NaOMe or Bu'NH2) is rearrangement, transposition of sulfur and oxygen giving Ph2P(O)NHSCOPh 7; this then reacts further, forming the phosphinic amide Ph2P(O)NH2 together with PhCO2Me or PhCONHBut. The re arrangement probably involves intramolecular nucleophilic displacement of benzoate by the P=S group of 6, forming an intermediate with P, N and S atoms in a three-membered ring.