光学活性香料化合物3-甲硫基己醇及其乙酸酯的制备  

Preparation of Optically Active Flavors 3-Methylthio Hexanol and Its Acetate

作　　者：余洁菲[1] 田红玉[1] 孙宝国[1] 欧阳天惠[1] 

机构地区：[1]北京工商大学化学与环境工程学院,北京100037

出　　处：《精细化工》2010年第4期369-373,共5页Fine Chemicals

基　　金：国家自然科学基金资助项目(20676003);北京市属高等学校人才强教计划资助项目(PHR201008244)~~

摘　　要：以(E)-2-己烯醛为起始原料,通过还原、Sharpless不对称环氧化、区域选择性还原、SN2亲核取代等反应制备光学活性的3-甲硫基己醇和3-甲硫基己基乙酸酯。首先(E)-2-己烯醛通过NaBH4还原得到(E)-2-己烯醇,产率91%。(E)-2-己烯醇通过Sharpless不对称环氧化,得到光学活性的2,3-环氧己醇,化学产率86%,产物ee值94%。2,3-环氧己醇用Red-Al进行区域选择性还原得到光学活性的1,3-己二醇,产率82%。将1,3-己二醇的伯羟基选择性转化为乙酸酯,3位羟基转化为甲磺酸酯,然后与自制的甲硫醇钾反应,经过SN2亲核取代反应后得到3-甲硫基己醇,三步反应总产率59%。3-甲硫基己醇用乙酸酐酯化得到3-甲硫基己基乙酸酯,产率87%。最终产物3-甲硫基己醇和3-甲硫基己基乙酸酯ee值均在94.0%左右。The syntheses of optically active 3-methylthio hexanol and 3-methylthio hexyl actetate were investigated starting from（E）-2-hexenal through reduction,the Sharpless asymmetric epoxidation,regioselective reduction and SN2 nucleophilic substitution.（E）-2-hexenal was reduced by NaBH4 to give（E）-2-hexenol in 91% yield.The optically active 2,3-epoxy hexanol was obtained through the Sharpless asymmetric epoxidation of（E）-2-hexenol with 94% eein 86% yield.2,3-Epoxy hexanol was regioselectively reduced with Red-Al to give optically active 1,3-hexanediol in 82% yield.After the primary hydroxy group of 1,3-hexanediol was transformed to acetate and 3-hydroxy was transformed to mesylate,an SN2 nucleophilic substitution by the reaction with self-made potassium thiomethoxide was carried out to form 3-methylthio hexanol.The overall yield of these three steps was 59%.3-Methylthio hexanol was esterified with acetic anhydride to give 3-methylthio hexyl acetate in 87% yield.The final products of 3-methylthio hexanol and 3-methylthio hexyl actate were obtained with about 94% ee.

关 键 词：3-甲硫基己醇 3-甲硫基己基乙酸酯 手性香料 不对称合成 

分 类 号：TQ225.24[化学工程—有机化工]