2,2,6,6-四羟甲基环己醇五烯丙基醚的合成

Synthesis of 2,2,6,6-tetrahydroxymethyl cyclohexanol allyl ether

以环己酮、甲醛为原料在碱催化下经羟醛缩合,康尼扎罗两步反应制得中间体2,2,6,6-四羟甲基环己醇。此化合物在季铵盐相转移催化下与氯丙烯反应生成2,2,6,6-四羟甲基环己醇五烯丙基醚。用红外光谱1、3C和1H核磁共振谱对2,2,6,6-四羟甲基环己醇和2,2,6,6-四羟甲基环己醇五烯丙基醚进行了表征。探讨了反应温度,催化剂用量,物料物质的量比等对2,2,6,6-四羟甲基环己醇和2,2,6,6-四羟甲基环己醇五烯丙基醚产率的影响。结果表明,合成2,2,6,6-四羟甲基环己醇的适宜条件为:n(碱)∶n(甲醛)∶n(环己酮)=1.25∶5.5∶1,羟醛缩合反应温度和反应时间分别为10℃和1 h,康尼扎罗反应温度和时间分别为40℃和1.5 h;合成2,2,6,6-四羟甲基环己醇五烯丙基醚的适宜条件为:n(氢氧化钠)∶n(氯丙烯)∶n(2,2,6,6-四羟甲基环己醇)=9∶10∶1,相转移剂用量为10%(以2,2,6,6-四羟甲基环己醇质量为基准),反应温度和时间分别为80℃和120 h,2,2,6,6-四羟甲基环己醇五烯丙基醚产率为58.3%。

2, 2, 6, 6-tetramethylolcyclohexanol （TMC） has been synthesized by consecutive aldol condensation and Cannizzaro reactions of cyelohexanone and formaldehyde with an alkaline catalyst. 2, 2, 6, 6-tetramethylol cyclohexanol allyl ether （TMAE） was subsequently prepared by reaction of TMC with allyl chloride using tetrabutylammonium bromide as phase transfer catalyst. The chemical structures of the products were confirmed by FT-IR,^ 1H NMR, and ^13C NMR spectroscopies. The effects of varying the temperature, the amount of catalyst, and the molar ratio of reactants on the yield of TMAE were investigated. A 58.3 % yield of TMAE was obtained by using the optimal reaction conditions as follows： n （alkali） ： n （formaldehyde） ： n （cyclohexanone） of 1.25 ： 5.5 ： 1, aldol condensation temperature of 10 ℃ and time of 1 hour, Cannizzaro reaction temperature of 40 ℃ and t.ime of 1.5 hours, n （sodium hydroxide） ： n （allyl chloride） ： n （TMC） of 9： 10： 1, weight of TBAB being 10% of that of TMC, reaction temperature of 80 ℃ and time of 120 hours.