2-己基-4-乙酰氧基四氢呋喃顺反异构体的制备  

Preparation of Trans-and Cis-2-Hexyl-4-acetoxytetrahydrofuran

作　　者：陈凯[1] 公秀琴[1] 孙宝国[1] 杨绍祥[1] 陈海涛[1] 田红玉[1] 

机构地区：[1]北京工商大学食品学院北京市食品风味化学重点实验室,北京100048

出　　处：《精细化工》2013年第8期906-910,914,共6页Fine Chemicals

基　　金：国家自然科学基金资助项目(31271932;31071610);国家科技部科技支撑计划项目(2011BAD23B01);北京市教委科技计划重点项目(KZ201110011015)~~

摘　　要：以烯丙基氯和庚醛为原料通过格氏反应制得1-癸烯-4-醇,产率86%;1-癸烯-4-醇用间氯过氧苯甲酸氧化,得到1,2-环氧-4-癸醇,产率89%;然后,在碳酸钾的作用下1,2-环氧-4-癸醇进行分子内的亲核取代反应,关环得到2-己基-4-羟基四氢呋喃顺反异构体的混合物,产率90%,trans-和cis-异构体比例为53∶47;2-己基-4-羟基四氢呋喃与对硝基苯甲酰氯反应,酯化产物通过柱层析分离,得到trans-和cis-2-己基-4-四氢呋喃对硝基苯甲酸酯,产率分别为52%和40%;分离后的酯化产物的顺反异构体在碱性条件下水解,得到trans-和cis-2-己基-4-羟基四氢呋喃,产率分别为85%和82%;trans-和cis-2-己基-4-羟基四氢呋喃与乙酸酐反应,得到trans-和cis-2-己基-4-乙酰氧基四氢呋喃,产率分别为83%和85%。trans-和cis-2-己基-4-乙酰氧基四氢呋喃经过GC-O进行了评香分析和稀释因子的测定,结果表明,两者具有不同的香气特征和香气强度。The preparation of c/s- and trans-2-hexyl-4-acetoxytetrahydrofuran has been studied. 1- Decen-4-ol was obtained in 86% yield by the Grignard reaction starting from allyl chloride and heptanal,which was then epoxidized by m-chloroperoxybenzoic acid to give 1,2-epoxy-4-decanol in 89% yield. The cis- and trans-2-hexyl-4-hydroxytetrahydrofuran mixture was produced in 90% yield through an intramolecular nucleophilic substitution of 1,2-epoxy-4-decanol promoted by K2CO3. The ratio of trans- to cis-isomer was 53：47.2-Hexyl-4-hydroxytetrahydrofuran reacted with p-nitrobenzoyl chloride and the products of esterification were separated by column chromatography to give trans- and cis-isomer individually in 52% and 40% yields respectively. The trans- or cis-ester was hydrolyzed in a basic solution to give trans- or cis-2-hexyl-4-hydroxytetrahydrofuran in 85% or 82% yield. Trans- or cis-2-hexyl-4-acetoxytetrahydrofuran was produced after acetylation with Ac2O in 83% or 85% yield. The odor and flavor dilution factor of trans- or cis-2-hexyl-4-acetoxytetrahydrofuran was evaluated by GC - O, which indicates that the two isomers differed in odor feature and intensity.

关 键 词：2-己基4-乙酰氧基四氢呋喃 顺反异构体 香气特性 香料 

分 类 号：TQ656.1[化学工程—精细化工]