Abstract
This communication describes the preparation of methoxy (4–6) and dimethylamino (7–9) derivatives of the reactive chlorodiazaphosphorinone heterocycles, 1–3, using trimethylsilylmethylether and trimethyldimethylaminosilane, respectively, as reagents. The methoxy compounds 4 and 5 were converted into the P(:O)Cl-derivatives 10 and 11 by reaction with sulfuryl chloride. The PNH(CH2CH2Cl) derivative 12 was obtained in the reaction of the phosphoryl chloride 11 with 2-chloroethylamine hydrochloride/triethylamine. The P(III) derivative 7 and the previously known compound 14 were oxidized to the phosphoryl (λ⌟P) species 13 and 15, using the urea/hydrogen peroxide 1:1 adduct. Finally, the oxidative addition of two molecules of hexafluoroacetone to 9, with formation of the perfluoropinacolyl spirophosphorane 16 is described. The characterization of the new compounds rests on their n.m.r. (1H-, 13C-, 19F-, and 31P-) spectral, and mass spectrometric data, in addition to elemental analyses.