Synthesis of tricyclic ( λ5 ) -phosphoranes N-demethylation/N-alkylation reactions during the oxidative addition perfluorinated α-diketones to P-bis(2-chloroethyl)amino-substituted λ3P-compounds

In the reaction of various 2,3-dihydro-1,3,2-benzodiazaphosphorin-4( 1 H )-ones with perfluorinated a-diketones, CF 3 C(:O)C(:O)R f an oxidative addition reaction with concomitant N -alkylation of the CH 3 (N) atom, and formation of tricyclic phosphoranes was found to take place. In one case no N -alkylation reaction was observed and a perfluoropinacolyl spirophosphorane was formed instead. The course of the reaction mainly depends on the steric demand of R f and the N -3 substituents of the benzodiazaphosphorinones.