B/L双酸性杂多酸杂化体催化的缩醛酮类香料合成  

Synthesis of acetal/ketal fragances catalyzed by Br?nsted/Lewis double acidic heteropolyacid hybrids

作　　者：沈小雄 李心忠 林棋 SHEN Xiaoxiong;LI Xinzhong;LIN Qi(College of Ocean,Minjiang University,Fuzhou 350108,Fujian,China;Fujian Engineering Research Center of New Chinese Lacquer Material,Fuzhou 350108,Fujian,China;Fujian Provincial University Engineering Research Center of Green Materials and Chemical Engineering,Fuzhou 350108,Fujian.China)

机构地区：[1]闽江学院海洋学院,福建福州350108 [2]福建省中国漆新型材料工程研究中心,福建福州350108 [3]绿色材料与化工福建省高校工程研究中心,福建福州350108

出　　处：《精细化工》2020年第3期555-560,共6页Fine Chemicals

基　　金：福建省自然科学基金(2017J10584);福建省教育厅科研项目(JK2016033);闽江学院科研项目(MJK18004)。

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BrΦnsted/Lewis双酸性杂多酸离子杂化体。离子杂化体为非均相催化剂,环己烷为带水剂,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-丙二醇经缩醛/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5类缩醛/酮香料,当n(杂多酸离子杂化体)∶n(醛/酮)∶n(乙二醇)=0.0012∶1∶1.5时,回流反应至无水/醇分出,目标化合物产率为80%~99%。杂化体经简单的过滤分离后即可循环使用,循环使用4次催化活性基本保持不变。A series of BrΦnsted/Lewis double acidic heteropolyacid based ionic hybrids were constructed by molecular self-assembly in the aqueous phase from double sulfonic acid functionalized quarternary ammonnium organic cation,transition metal ions and Keggin configuration heteropolyacid(H4 SiW12 O40 and H3 PW12 O40).These ionic hybrids were acted as heterogeneous catalysts to synthesized a series of acetal/ketal fragrances by acetal/ketone reaction of benzaldehyde,cyclohexanone,ethyl acetoacetate and methyl acetoacetate with ethylene glycol,1,2-propanediol,1,3-propanediol using cyclohexane as watercarrying agent.It was founded that when n(hybrid)∶n(aldehyde/ketone)∶n(glycol)=0.0012∶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 yields of 80%~99%,respectively.After simple filtration and separation,the ionic hybrid could be recycled,and its catalytic activity remained unchanged after 4 cycles of recycling.

关 键 词：杂多酸 离子杂化体 缩醛/酮 苹果酯 草莓酯 风信子素 香料 

分 类 号：TQ651.1[化学工程—精细化工] TQ426.91