乙酸氧钒催化α-蒎烯与过氧化氢烯丙位氧化的介质效应  

Media Effects in Allylic Oxidation of α-Pinene with Hydrogen Peroxide Catalyzed by VO( OAc)_2

作　　者：郑敏[1] 寻有益 周硕林[2] 肖毅[2] 徐琼[2] 尹笃林[2] ZHENG Min;XUN You-yi;ZHOU Shuo-lin;XIAO Yi;XU Qiong;YIN Du-lin(Hunan First Normol University, Changsha 410205, China;National ＆ Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources , Hunan Normal University , Changsha 410081, China)

机构地区：[1]湖南第一师范学院,湖南长沙410205 [2]湖南师范大学石化新材料与资源精细利用国家地方联合工程实验室,湖南长沙410081

出　　处：《分子催化》2018年第2期174-179,共6页Journal of Molecular Catalysis(China)

基　　金：湖南省教育厅青年项目(15B050);湖南省科技厅重点研发计划(2015NK3029);国家自然科学基金(21776068和21003043)~~

摘　　要：以乙酸氧钒为催化剂,过氧化氢为氧化剂,研究了α-蒎烯的氧化反应.考察了以4个碳原子的有机物丁酮、乙二醇二甲醚、乙酸乙酯、1,4-二氧六环、四氢呋喃、叔丁醇和二氯甲烷作为溶剂构成反应介质,以及溶剂用量、反应温度和反应时间等因素对催化性能的影响,发现在醚类和乙酸乙酯中乙酸氧钒对α-蒎烯与过氧化氢的烯丙位氧化具有优良催化作用.结果表明,在催化剂用量为10.0%、反应温度为40℃、乙二醇二甲醚为溶剂、反应8 h时α-蒎烯转化率达82.9%,主要烯丙式氧化产物的选择性达73.5%,其中马鞭草烯酮、马鞭草烯醇和龙脑烯醛的选择性分别为45.9%、17.3%和10.3%.VO（ OAc）2 was synthesized and used as catalyst for the oxidation of α-pinene using H2O2 as oxidant.The effects of reaction media such organic compound with four carbon atoms,butanone,ethylene glycol dimethyl ether,ethyl acetate,dichloromethane,1,4-dioxane,tetrahydrofuran and tert.-butyl alcohol as solvent,also amount of solvent,temperature,amount of catalyst and time on catalytic performance were investigated. It is found that vanadyl acetic posses fine catalytic performance for the allylic oxidation of α-pinene in ethers or ethyl acetate. The results showed that under optimized reaction conditions of w（ catalyst） = 10% ,at 40 ℃ for 8 h,using ethylene glycol dimethyl ether as solvent,the conversion of α-pinene reached 82.9% with selectivity 45.9% for verbenone,17.3% verbenol and 10.3% campholene aldehyde.

关 键 词：乙酸氧钒 Α-蒎烯 过氧化氢 催化 氧化 

分 类 号：O643.36[理学—物理化学]