Oxime derivatives and reactions of hexakis (4-acylphenoxy) cyclotriphosphazenes

In this study, hexachlorocylotriphosphazene (1) was reacted with 4-hydroxybenzaldehyde and 4-hydroxyacetophenone. From these reactions, hexakis(4-formylphenoxy) cyclotriphosphazene (2) and hexzakis(4-acetylphenoxy)cyclotriphosphazene (13) were obtained. SinceJıexaclık>r£«ıylo1riphosph^ene is sensi^ejo^a^andmoistoe.1 experimental studies were carried out at without air and moisture in argon atmosphere. Compounds 3 and 14 were synthesized from the reactions of 2 and 13 with hydroxlaminehydrochloride in pyridine, respectively. Compound 3 was reacted with acetyl chloride, chloroacetyl chloride, ethyl bromide, allyl bromide, benzyl chloride, propyl chloride, propanoyl chloride, benzenesulfonyl chloride, napthalenesulfonyl chloride, benzoyl chloride, methyl iodide, 4-methoxybenzoyl chloride, 2- chlorobenzoyl chloride, 2-chlorobenzyl chloride, 4-chlorobenzyI chloride, monochloroacetone, 1,4-dichlorobutane, diethylbromomalonnoate and methacriloyl chloride. Hexasubstituted compounds were obtained from the reactions of 3 with acetyl chloride, chloroacetyl chloride, ethyl bromide, allyl bromide, benzyl chloride and chloride via all of the oxime protons replacement with alkyl or aryl groups. Howewer, tetrasubstituted and pentasubstituted products formed from the reactions of 3 with methyl iodide and benzoyl chloride, respectively. It was observed that the oxime groups on 3 rearranged to nitrile in the reactions of 3 with benzenesulfonyl chloride, napthalenesulfonyl chloride and methacriloyl chloride. Pure and defined products were not obtained from the reaction of 3 with propyl chloride, 4-methoxybenzoyl chloride, 2-chlorobenzoyl chloride, 2-chlorobenzyl chloride, 4- chlorobenzyl, chloride, monochloroacetone, 1,4-dichlorobutane and diethylbromomalonnoate. _f{ >?f~'\ XII %*.%.Compound 14 was reacted with acetyl chloride, chloroacetyl chloride, ethyl bromide, allyl bromide, benzyl chloride, propyl chloride, propanoyl chloride, benzenesulfonyl chloride, napthalenesulfonyl chloride, benzoyl chloride, methyl iodide, 4-methoxybenzoyl chloride, 2- chlorobenzoyl chloride, 2-chlorobenzyl chloride, 4-chlorobenzyl chloride, monochloroacetone, 1,4-dichlorobutane, diethylbromomalonnoate and acriloyl chloride. Hexasubstituted compounds were obtained from the reactions of 14 with 4- methoxybenzoyl chloride, 2-chlorobenzoyl chloride, propanoyl chloride, allyl bromide and benzoyl chloride via all of the oxime protons replacement with alkyl or aryl groups. Howewer, trisubstituted products formed from the reactions of 14 with benzyl chloride and chloroacetyl chloride, tetrasubstituted compounds from ethyl bromide and acetyl chloride, and pentasubstituted compound from acriloyl chloride. Pure and defined products were not obtained from the reaction of 14 with propyl chloride, benzenesulfonyl chloride, napthalenesulfonyl chloride, methyl iodide, 2-chlorobenzyl chloride, 4- chlorobenzyl chloride, monochloroacetone, 1,4-dichlorobutane and diethylbromomalonnoate. The structure of the compounds were defined by elementel analysis, IR, 'H, 13C, and 31P- NMR spectroscopy. KEYWORDS: Hexachlorocyclotriphosphazene, phosphazene, cyclophosphazene, oxime, oxime derivatives.