1,3-二(5,5-二甲基-1,3-二氧杂己内磷酰氧基)苯合成方法的改进

以新戊二醇、三氯氧磷和间苯二酚为原料,三乙胺为缚酸剂从另外一条路线合成了1,3-二(5,5-二甲基-1,3-二氧杂己内磷酰氧基)苯,即新戊二醇先与三氯氧磷反应制得新戊二醇磷酰氯,再以该磷酰氯与间苯二酚反应制得目标产物。其适宜的反应条件为:n(新戊二醇磷酰氯)∶n(间苯二酚)∶n(三乙胺)=2∶1∶4,回流温度(~64℃)下反应时间为4 h,以间苯二酚计的目标产物收率为66.2%。产物结构通过IR、NMR分析进行了确认。与1998年的5 852 197号美国专利方法相比,该法降低了原料三氯氧磷的用量,省去了蒸馏过量三氯氧磷的操作,收率提高了20.9%。

Improvement on Synthesis of 1,3-Bis(2-oxo-5,5-dimethyl-1,3,2-dioxaphos-phorinanyl-2-oxy) benzene

A new synthesis route was developed to prepare 1,3-bis(2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinanyl-2-oxy)benzene from neopentyl glycol,phosphorus oxychloride and resorcinol in the presence of triethylamine as acid-binding agent.Thus,neopentyl glycol chlorophosphate was obtained at first by reaction of neopentyl glycol with phosphorus oxychloride,and then the chlorophosphate,resorcinol and triethylamine in mole ratio 2∶1∶4 reacted under reflux(~64 ℃) for 4 h to give the title compound in 66.2% yield.Structure of the title compound was confirmed by IR and NMR spectra.Compared with the literature methods(US(5 852 197),1998),the consumption of phosphorus oxychloride was decreased,the recovery procedures of excessive phosphorus oxychloride were no longer necessary,and the yield was increased by 20.9%.