Darstellung von 5,6-Benzo-1,3-dialkyl-2-P-substituierten 1,3,2-Diazaphosphorinan-4-onen; Einkristall-Röntgenstrukturanalysen von 2-fluorsubstituierten 1,3,2λ 4-Benzodiazaphosphorinanon-Derivaten

Abstract

The reactions of the 5,6-benzo-2-chloro-1,3-dimethyl- or 1-methyl-3-(2-chloroethyl)-1,3,2λ 3-diazaphosphorinan-4-ones 1 and 2 with the triethylamine · 3HF adduct in a molar ratio 3:1 in the presence of excess triethylamine furnished the 2-fluorosubstituted 1,3,2λ 3-diazaphosphorinanones 3 and 4 in good yield. In the reactions of 1 and 2 with trimethylsilylmethyl ether or methanol in the presence of free triethylamine, the 2-methoxy-substituted-1,3,2λ 3-benzodiazaphosphorinan-4-ones 5 and 6 were formed. Oxidation of 3 and 4 to the 2-fluoro-2-oxo-1,3,2λ 4-benzodiazaphosphorinanones 7 and 8 was effected either by aqueous hydrogen peroxide or by the hydrogen peroxide-urea 1:1 adduct. Furthermore, substitution of the 2-chloro-2-oxo-1,3,2λ 4-benzodiazaphosphorinanones 9 and 10 with the triethylamine·3HF adduct in a molar ratio of 3:1 in the presence of excess triethylamine furnished the corresponding derivatives 7 and 8, involving λ 4-phosphorus. The phosphoryl chloride derivatives 9 and 10 were obtained in the reaction of the 2-P-methoxy derivatives 5 and 6 with sulfuryl chloride. Compounds 9 and 10 were allowed to react with the amine derivatives, 2-chloroethylamine hydrochloride and bis(2-chloroethyl)amine hydrochloride, in the presence of triethylamine in a molar ratio of 1:2, forming the λ 4-phosphorus derivatives 11-13. Characterization of 3-13 was based on their NMR spectra and mass spectra. X-Ray structure determinations of 7 and 8 are described. In both structures the phosphorus atom has a distorted tetrahedral coordination geometry. The six-membered heterocycle of 7 displays an envelope conformation with the phosphorus atom out of plane, whereas the heterocycle of 8 displays a distorted envelope conformation with the phosphorus atom and one nitrogen atom out of plane.