聚离子液体杂多酸离子杂化体催化的环酮Baeyer-Villiger氧化  

Baeyer-Villiger oxidation of cyclic ketone catalyzed by poly(ionic liquids)polyoxometalated ionic hybrid

作　　者：庄玉静 郑良东 李心忠 ZHUANG Yu-jing;ZHENG Liang-dong;LI Xin-zhong(College of Ocean,Minjiang University,Fuzhou 350108,China;Green Materials and Chemical Engineering Research Centre of Fujian Province University,Fuzhou 350108,China;Fujian Engineering Research Center of Chinese Lacquer Material,Fuzhou 350108,China)

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

出　　处：《化学研究与应用》2021年第5期825-832,共8页Chemical Research and Application

基　　金：福建省自然科学基金项目(2017J10648)资助;闽江学院科研项目(MYK19010)资助;闽江学院校长基金项目(103952019098)资助。

摘　　要：以N,N-二甲基甲基丙烯酸乙酯、氯乙酸、磷钨酸、硅钨酸为起始原料,经季铵化、自由基聚合、分子自组装,构建了两种羧基官能化聚离子液体杂多酸离子杂化体COOH-PIL@P-POM和COOH-PL@Si-POM,离子杂化体同时具有表面两亲活性、氧化催化活性和多孔性质,以其为非均相催化剂、工业级过氧化氢为氧化剂,实现了环酮的Baeyer-Villiger氧化,当n(离子杂化体)∶n(环酮)∶n(过氧化氢)=0.0005∶1∶3.0时,1,2-二氯乙烷为溶剂,反应温度60℃,反应时间4h,对应的环内酯产率59.6~90.5%。离子杂化体经离心分离、溶剂洗涤、真空干燥即可再生循环使用,循环使用5次,催化活性基本保持不变。Two carboxylic acid functionalized poly(ionic liquids)and heteropoly acid ionic hydrids were synthesized using N,N-dimethylallyamine,chloroacetic,H3PW12O40 and H4SiW12O40 as starting materials via quaternization,free-radical polymerization and self-assembly in water.These compounds exhibited amphiphilic and oxidative catalytic activity and porous property at the same time,which acted as efficient recyclable catalysts realized Baeyer-Villiger oxidation of the cyclic ketone into lactone using 30%H_(2)O_(2) as oxidant.When the molar ratio of n(ionic hybrids)∶n(cyclic ketone)∶n(H_(2)O_(2))=0.0005∶1∶3.0,1,2-dichloroethane as solvent,reaction temperature was 60℃,reaction time was 4h,the lactone was obtained with yield ranging from 59.6 to 90.5%.Two ionic hybrids could be recovered and reused by simple workup,there were no significant decline in yield after recycling for 5 times.

关 键 词：聚离子液体 杂多酸 BAEYER-VILLIGER氧化 环酮 环内酯 

分 类 号：O624.4[理学—有机化学]