Summary In trifluoromethanesulphonic acid (HTFMS) the P-hT bond of (RO),P(O)NMe, is stable, but de-0- alkylation is observed ; rates of the oxygen-alkyl cleavage of phosphoramidates and some other phosphoryl com- pounds in HTFMS have been determined. ... Under these conditions however, slow demethylation takes place (reaction 1). Reaction (1) can be easily followed by ... HTFMS (MeO),P(O)NMe, ------+ (HO),P(O)NMe, + 2 Me-TFMS (1) (1)