Synthesis and characterization of benzyl and benzoyl substituted oxime-phosphazenes

Abstract

Two oxime-cyclophosphazenes were prepared from hexakis(4-formylphenoxy)cyclotriphosphazene ( 2) and hexakis(4-acetylphenoxy)cyclotriphosphazene ( 7). The reactions of these oximes with benzyl chloride, benzenesulfanoyl chloride, benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride were studied. Hexa and pentasubstituted compounds were obtained from the reaction of hexakis(4-[(hydroxyimino)methyl]phenoxy)cyclotriphosphazene ( 3) with benzyl chloride ( 4) and benzoyl chloride, respectively. However, the oxime groups on 3 rearranged to nitrile ( 5) in the reaction of 3 with benzenesulfanoyl chloride and 1-napthalenesulfanoyl chloride. Hexasubstituted compounds were also obtained from the reactions of hexakis(4-[(1)- N-hydroxyethaneimidoyl]phenoxy)cyclotriphosphazene ( 8) with benzoyl chloride ( 10), 4-methoxybenzoyl chloride ( 11) and 2-chlorobenzoyl chloride ( 12). A trisubstituted compound was obtained from the reaction of 8 with benzyl chloride ( 9). All the products were generally obtained in high yields. Pure and defined products could not be obtained from the reaction of 3 with 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. The structures of the compounds were defined by elemental analysis, IR, 1H, 13C and 31P NMR spectroscopy.