B/L双酸性杂多酸离子杂化体催化的缩醛酮类香料合成研究

Synthesis of Acetal/ketal Fragrancy Catalyzed by Br?nsted/Lewis Double Acidic Polyoxometalated-based Ionic Hybrids

摘要:

以双磺酸基官能化线性结构季铵有机离子、过渡金属离子与Keggin构型杂多酸H4SiW12O40、H3PW12O40为合成子， 在水相中经分子自组装，构建了系列Br?nsted/Lewis双酸性杂多酸离子杂化体。离子杂化体为非均相催化剂，由苯甲醛、环己酮、乙酰乙酸乙酯、乙酰乙酸甲酯与乙二醇、1，2-丙二醇、1，3-丙二醇，环己烷为带水剂缩醛/酮反应，合成了系列苯甲醛缩醛、环己酮缩酮、苹果酯和草莓酯；由苯乙醇、乙缩醛缩合脱醇合成了风信子素五种缩醛/酮类香料，当n(杂多酸离子杂化体：n(醛/酮)：n(二元醇)=0.012：1：1.5时，回流反应至无水/醇分出， 目标化合物产率80-99%。杂化体经简单的过滤分离后即可循环使用，循环使用5次催化活性基本保持不变。

Abstract:

A series of sulfonic acid functionalized Br?nsted/Lewis double acdic heteropoly acid based ionic hybrids were synthesized using double sulfonic acid functionalized quarter amunium organic cation, transition metal ions and Keggin type H4SiW12O40、H3PW12O40 as construction unit via molecular self-assembly in water. These compounds acted as catalysts in synthesis of acetal/ketal fragrancy were studied, and founded that the mole ration of ionic hybrid:keton/aldehyde or phenylethyl alcohol :diol or aectal is 0.012:1:1.5, under reflux condition until to no water or alcohol production, a series of benzaldehyde acetal, cyclohexanone ketal, fructone,fraistone and hyacinth body were obtained with yield of 80-99% re-spectively. Ionic hybrid could be recovered and reused by simple filtration, there are no significant decline in yield activity after recycling for 5 times.