DARSTELLUNG VON 2-CHLOROXAZAPHOS PHORINANONEN; OXIDATIVE ADDITIONS TETRACHLOR-O-BENZOCHINON; SYNTHESE VON DICHLORO-Pt(II)-KOORDINATIONS VERBINDUNGEN 2-CYANSUBSTITUIERTER BENZODIAZA-UND BENZOXAZAPHOS PHORINANON-DERIVATE

Abstract

The reaction of the chloro-substituted o-aminobenzoic acids 1–3 with phosphorus trichloride led to the P-chlorobenzoxaza-substituted derivatives 4–6. The reaction of the previously known 5,6-benzo-2-chloro-1,3-dimethyl-1,3,2-diazaphosphorinan-6-one 7 with trimethylsilylcyanide furnished the P-cyano derivative 8. Its structure was confirmed by a single-crystal X-ray Structure analysis. The phosphorus atom lies out of the plane of the other atoms of the heterocycle and displays a short intermolecular P–O contact. Oxidative addition of tetrachloroorthobenzoquinone (TOB) at the A⁵P atom of 8, 9 and 12 gave the λ⁴-and λ⁵-P-compounds 10, 11 and 13, respectively. 5,6-Benzo-2-cyano-1,3-dimethyl-1,3,2-diazaphosphorinan-6-one 8 and 4,5-benzo-2-cyano-3-methyl-1,3,2-oxazaphosphorinan-6-one 9 reacted with dichloro(cycloocta-1,5-diene)platinum(II) [(COD)PtCl₂] with formation of the 1:1 complexes 15 and 16. In the reaction of 8 with hexafluoroacetone (HFA) the unusual ester derivative 17 was formed. The characterization of 4–17 is based on ¹H-, ¹³C-, and ¹³P-NMR-spectra, mass spectra and elemental analysis.

Key Words:

• 1,3,2-Benzodiazaphosphorinanones
• 1,3,2-benzoxazaphosphorinanones
• oxidative addition