一种制备(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇的新方法  

A Novel Method for Preparation of (3R,4R)-4,7,7-Trimethyl-6-oxabicyclo[3. 2. 1] octane-3,4-diol

作　　者：黄道战[1,2] 朱守记 蓝虹云 雷福厚 

机构地区：[1]广西民族大学化学化工学院 [2]广西林产化学与工程重点实验室,广西南宁530008

出　　处：《林产化学与工业》2015年第1期9-15,共7页Chemistry and Industry of Forest Products

基　　金：广西科学研究与技术开发计划项目(1348006-10);广西自然科学基金(2011GXNSFA018057);广西民族大学引进人才科研启动项目(2010QD020)

摘　　要：在催化剂过氧磷钨酸十二烷基吡啶盐(Cat-PW4)的作用下,α-蒎烯与H2O2反应生成主要产物(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇。不同反应条件对反应转化率和选择性的实验结果表明,最佳反应条件为:12.8 mmolα-蒎烯、5 m L溶剂三氯甲烷、0.2 g催化剂、3.3 m L 30%H2O2,反应温度40℃,反应时间3 h,α-蒎烯转化率和产物的选择性分别为94.7%和39.8%。反应结束后,该产物存在于水相和有机相中,通过萃取和重结晶分离提纯,得率11%,纯度达到98%;其分子结构通过红外光谱、紫外光谱、1H核磁共振谱、13C核磁共振谱、低分辨率质谱及高分辨率质谱确证。（ 3R,4R）-4,7,7-trimethyl-6-oxabicyclo [3. 2. 1] octane-3,4-diol was prepared by reaction of α-pinene with 30 %H2O2in presence of dodecyl pyridinium peroxyopolyphosphotungstate catalyst（ Cat-PW4）. The effects of different reaction factors on the conversion rate and selectivity were investigated. The optimal conditions are as follows： α-pinene,12. 8 mmol; chloroform as solvent,5 mL; reaction temperature,40 ℃; Cat-PW4 as catalyst,0. 2 g; 30 % H2O2,3. 3 mL; reaction time,3 h. Under these conditions,the conversion rate of α-pinene reached 94. 7 %,and the selectivity for the title compound reached 39. 8 %.The product existed both in aqueous phase and organic phase and could be isolated from reaction mixtures by extraction and recrystallization. It was structurally identified by means of IR,UV,^1H NMR,^13 C NMR,GC / MS,and HR-ESI-MS. Its yield and purity were 11 % and 98 %,respectively.

关 键 词：(3R 4R)-4 7 7-三甲基-6-氧杂二环[3.2.1]辛烷-3 4-二醇 Α-蒎烯 H2O2 过氧磷钨酸十二烷基吡啶盐 

分 类 号：TQ351[化学工程]