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.