Synthesis Of New Chlorophosphazene Compounds

Phosphazenes contain-P=N-units in their chemical structures.The variety of substitution reactions on the reactive P-Cl bonds make cyclop-hosphazenes a wide range of derivatives which have diverse applications.Their derivatives are usually prepared by nucleophilic substitution reacti-ons of alcohol,phenol,amines,Grignard reagents,and thiols.In recent years,cyclophosphazenes have been widely studied.In this paper,three types of cyclophosphazenes derivatives were designed and synthesized.Hexakis（4-（1-acetyl）phenoxy）cyclotriphosphazene was obtained from the reaction of hexachlorocyclotriphosphazene with 4-hydroxy-acetophenone.The hexakis（4-[1-（hydroxyimino）ethyl]-phenoxy）cyclo-triphosphazene was synthesized from the reaction of hexakis（4-（1-acetyl）phenoxy）cyclotriphosphazene with hydroxylaminehydrochloride in pyridine.The novel oxime-cyclophosphazene derivatives were synthesized from hexakis（4-[1-（hydroxyimino）ethyl]-phenoxy）cyclo-triphosphazene via electrophilic reaction with benzoyl chloride,benzyl chloride,chloroacetyl chloride,4-methoxybenzoyl chloride and 2-chloro-benzoylchloride.All products were generally obtained in high yields.Their structures were confirmed by MS,¹H NMR and ¹³C NMR.Tetrachloro（2,2’-dihydroxybiphenyl）cyclotriphosphazene was got from the reaction of hexachlorocyclotriphosphazene with 2,2’-dihydroxy-biphenyl.Tetrachloro（2,2’-dihydroxybiphenyl）cyclotri phosphazene reacted with 4-hydroxyacetophenone resulting in tetra（4-（1-acetyl）phen-oxy）（2,2’-dihydroxybiphenyl）cyclotriphosphazene.Tetrachloro（2,2’-dihy-droxybiphenyl）cyclotriphosphazene reacted with 4-hydroxypropiopheno-ne resulting in tetra（4-（1-propionyl）phenoxy）-（2,2’-dihydroxybiphen-yl）-cyclotriphosphazene.The two novel oxime-cyclophosphazenes contain-ing dioxybiphenyl group was synthesized from the reaction of tetra（4-（1-acetyl）phenoxy）-（2,2’-dihydroxybiphenyl）cyclotriphosphazeneor tetra（4-（1-propionyl）phenoxy）（2,2’-dihydroxybiphenyl）cyclotriphospha-zene with hydroxylaminehydrochloride in pyridine.The reactions of this oxime-cyclophosphazenes with benzoyl chloride,allyl bromide,chloro-acetyl chloride,4-methoxybenzoyl chloride and 2-chlorobenzoylchloride were studied.The structures of the compounds were confirmed by MS,¹H NMR and ¹³C NMR spectroscopy.2,2-Dichloro-4,4,6,6-bis[spiro（2’,2”-dioxy-1’,1”-biphenylyl）]cyclotr iphosphazene was synthesized from the reaction of hexachlorocyclotri-phosphazene with biphenyl-2,2’-diol.2,2-Bis（4-formylphenoxy）-4,4,6,6-bis[spiro（2’,2”-dioxy-1’,1”-biphenylyl）]cyclotriphosphazene was obtain-ed from the reaction of 2,2-dichloro-4,4,6,6-bis[spiro（2’,2”-dioxy-1’,1”-biphenylyl）]cyclotriphosphazene with 4-hydroxybenzaldehyde.2,2-Bis-[4-（4-quinazolinone）phenoxy]-4,4,6,6-bis[spiro（2’,2”-dioxy-1’,1”-biphen ylyl）]cyclotriphosphazene was synthesized from the reaction of 2,2-bis（4-formylphenoxy）-4,4,6,6-bis[spiro（2’,2”-dioxy-1’,1”-biphenylyl）]cyclotrip hosphazene with anthranilamide in N,N-dimethylformamide.The novel cyclophosphazene derivatives were synthesized from the reaction of 2,2-bis[4-（4-quinazolinone）phenoxy]-4,4,6,6-bis[spiro（2’,2”-dioxy-1’,1”-biphenylyl）]cyclotriphosphazene with 4-chlorobenzenemethanethiol,p-thiocresol,4-aminothiophenol,and 4-chlorothiophenol in the presence of p-toluenesulfonyl chloride via C-OH bond activation under mild conditions.All products were generally obtained in high yields.Their structures were characterized by HRMS,IR and ¹H,¹³C spectroscopy.