一步法合成二亚磷酸三(2,2'-联苯酚)酯

以三氯化磷和2,2'-联苯酚为原料,一步法合成了二亚磷酸三(2,2'-联苯酚)酯,通过质谱及核磁共振等方法对产品进行了表征,证实产品为目标化合物且纯度很高。考察了三乙胺用量、溶剂种类、反应时间以及反应温度等因素对产品收率的影响。最佳反应条件为:以氯仿为溶剂,n(三氯化磷)∶n(2,2'-联苯酚)∶n(三乙胺)=1∶1.5∶3.5,25℃下反应15 h。在此条件下制得的产品为白色晶体,收率为89.7%。对可能发生的副反应进行了探讨,当反应程度过低时,会生成含氯的副产物;而当反应过于剧烈时,生成三亚磷酸酯等副产物的几率增大。

Direct Synthesis of 2,2'-Bis ( Dibenzo [ d, f] [ 1,3,2 ] Dioxaphosphepin-6-yloxy) Biphenyl

2,2′-bis(dibenzo [d,f][1,3,2] dioxaphosphepin-6-yloxy)biphenyl was synthesized directly by reaction between PCl3 and 2,2′-biphenol in the presence of triethylamine(Et3N) which could react with HCl produced in the reaction.Structure of the product was confirmed by means of MS and NMR.The influences of mole ratio of Et3N to PCl3,solvent type,reaction temperature and reaction time on the reaction were studied.Under the appropriate reaction conditions of chloroform as solvent,n(PCl3) ∶ n(2,2′-biphenol) ∶ n(Et3N) 1 ∶ 1.5 ∶ 3.5,reaction temperature 25 ℃ and reaction time 15 h,the white crystalline product was obtained and its yield was 89.7%.The probable side reactions were investigated.When the reaction is inadequate,Cl-contained by-products may be obtained.If the reaction is excessive,multi-phosphites may be produced.