含氮化合物硝酸盐催化2,10-环氧蒎烷液相重排反应的研究  

Study on Liquid Phase Rearrangement of 2,10-Epoxypinane Catalyzed by Nitrate of Nitrogen-containing Compounds

作　　者：彭沙[1] 李谦和[1] 匡玲玲[1] 李雪辉[2] 王乐夫[2] 

机构地区：[1]湖南师范大学精细催化合成研究所,长沙410081 [2]华南理工大学化工学院,广州510640

出　　处：《湖南城市学院学报（自然科学版）》2006年第4期47-50,共4页Journal of Hunan City University:Natural Science

基　　金：国家自然科学基金资助项目(200146001;20206010);广东省自然科学基金资助项目(031419;203C33503)

摘　　要：研究了含氮化合物硝酸盐催化的2,10-环氧蒎烷液相重排反应的产物分布和反应机理,考察了催化剂、溶剂和反应温度对重排产物分布的影响.结果表明:2,10-环氧蒎烷的液相重排反应主要生成紫苏醇和桃金娘烯醇,产物中紫苏醇和桃金烯醇的含量达到80%以上;2,10-环氧蒎烷的液相重排反应是按碳正离子机理进行的,反应底物与质子酸H+形成的氧鎓离子转化成碳正离子中间体,再经2条途径分别生成紫苏醇和桃金娘烯醇,催化剂活性位的Bronsted酸强度和空间结构是影响重排产物分布的主要因素,并对提出的反应机理进行了讨论.The product distributions and reaction mechanism of liquid-phase isomerization of 2,10-epoxypinane catalyzed by nitrate of nitrogen-containing compounds was studied. The influence of catalysts, solvents and reaction temperature on the product distributions was investigated emphatically. Experimental results indicated that the liquid-phase isomerization of 2,10-epoxypinane catalyzed by nitrate of nitrogen-containing compounds produced mainly two monoterpenyl alcohol---perilla alcohol and myrtenol and the total content of the two monoterpenyl alcohol was over 80%. The isomerization reaction was carried out according to the typical carbocation mechanism, and the protonium ion intermediate, formed by the reacting substance with Bronsted acid H~, decomposed via two approach to form perilla alcohol and myrtenol. The acidity of active site of catalysts and its spatial configuration were the dominant factors affected on the product distributions. The reaction mechanism of isomerization was also discussed.

关 键 词：2 10-环氧蒎烷 液相重排 酸催化剂 反应机理 

分 类 号：TQ351.014[化学工程]