Synthesis of symmetrical bis-(2-chloro-1,3,2-benzodiazaphosphorinones) hydrolysis and fluorination of selected compounds

The series of symmetrical bis-amides 3 was formed by the reaction of N-meth ylisatoic anhydride (1), with the diamines 2. Reaction of 3 with phosphorus trichloride led to the formation of the symmetrical bis-(1,3,2-benzodiazap hosphorinones) (4). 4c, 4d and 4e were easily hydrolyzed in moist air, lead ing to the formation of 5c,5d and 5e. In the presence of triethylamine, 4c, 4d and 4e were allowed to react with Et3N . 3HF to give the symmetrical bi s-P-F derivatives 6c, 6d and 6e, which could be readily oxidized by (NH2)(2 )C(:O). H2O2, leading to the formation of a series of P(:O)F compounds 7c, 7d and 7c. All compounds were characterized unambiguously by H-1, C-13, F-1 9, and P-31-NMR-spectroscopy, mass spectrometry, and elemental analysis. Al l the bis-amides and bis-(1,3,2-benzodiazaphosphorinones), except 4b and 4f , exist as single conformers in common solvents such as toluene, diethyl et her, dichloromethane or chloroform. For compound 6c, a single crystal X-ray structure analysis was conducted. The molecule displays crystallographic i nversion symmetry.