PEG6000-OSO_3H催化下酮类的Baeyer-Villiger氧化反应  

Baeyer-Villiger Oxidation of Ketones Catalyzed by PEG6000-OSO_3H

作　　者：杨志旺[1] 牛棱渊[1] 马振宏[1] 康巧香[1] 石星丽[1] 雷自强[1] 

机构地区：[1]西北师范大学化学化工学院生态环境相关高分子材料教育部重点实验室,甘肃兰州730070

出　　处：《精细化工》2011年第1期59-63,73,共6页Fine Chemicals

基　　金：国家自然科学基金项目(20774074);甘肃省自然科学基金项目(3ZS061-A25-018);西北师范大学创新基金培育项目(NWNU-KJCXGC-03-56)~~

摘　　要：制备了PEG6000负载氯磺酸催化剂（PEG6000-OSO3H）,利用FTIR、TG和元素分析方法对催化剂进行了表征。研究了以PEG6000-OSO3H为催化剂,质量分数30%的H2O2为氧化剂条件下,酮类的Baeyer-Villiger氧化反应,考察了溶剂、反应温度、反应时间、催化剂用量、氧化剂用量等因素对反应的影响,得到反应的最佳条件为：底物酮0.1 mmol,质量分数为30%的H2O20.3 mmol,催化剂用量10 mg,溶剂1,2-二氯乙烷3 mL,温度70℃,反应时间24 h。在该条件下,一些环酮类底物如2-金刚烷酮、环戊酮、环己酮、2-甲基环己酮、4-甲基环己酮和4-叔丁基环己酮等都可以在温和的条件下被氧化得到相应内酯,且反应具有89%~100%的底物转化率和80%~99%的内酯选择性。通过柱层析方法分离了产物,并进行了1HNMR和13CNMR波谱确证。PEG6000-OSO3H was prepared and characterized by FTIR,TG and elementary analysis.The Baeyer-Villiger oxidation of ketones catalyzed by PEG6000-OSO3H with w（H2O2）=30% solution as oxidant was investigated.The influences of solvents,reaction time,temperature,dosage of catalyst and the oxidant on the catalytic activity are well investigated.The optimizing conditions were concluded as：0.1 mmol ketones solved in 3 mL 1,2-dichloroethane and oxidized by 10 mg PEG6000-OSO3H with 0.3 mmol of 30%H2O2 at 70 ℃ for 24 h.Under the optimum condition,a series of cyclic ketones such as 2-adamantanone,cyclopentanone,cyclohexanone,2-methylcyclohexanone,4-methylcyclohexanone and 4-tert-butylcyclohexanone were well transformed into the corresponding lactones with the conversion of 89%～100% and the selectivity of 80%～99%,respectively.Some of the products were purified by a silica gel column and characterized by NMR spectra.

关 键 词：PEG6000-OSO3H 催化 BAEYER-VILLIGER氧化 H2O2 负载 

分 类 号：TQ426[化学工程] O643.32[理学—物理化学]