DARSTELLUNG UND CHARAKTERISIERUNG VON 2-AMINO- UND 2-METHOXYSUBSTITUIERTEN BENZODIAZAPHOSPHORINONEN MIT PHOSPHOR IN DEN KOORDINATIONSZAHLEN DREI, VIER UND FÜNF

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.

Key Words:

• 1,3,2-benzodiazaphosphorin-4-ones
• halogen substitution
• rearrangement
• oxidation reactions
• spirophosphoranes