一种新的α-(2-甲基-3-呋喃硫基)酮类香料化合物的制备方法  

A new method of preparingα-(2-methyl-3-furylthio)ketones as flavors

作　　者：王亚玲[1] 田红玉[1] 孙宝国[1] 余洁菲[1] 

机构地区：[1]北京工商大学化学与环境工程学院,北京100048

出　　处：《日用化学工业》2010年第6期448-451,共4页China Surfactant Detergent & Cosmetics

基　　金：国家自然科学基金资助项目(31071610);北京市属高等学校人才强教计划资助项目(PHR201008244和PHR20090504)

摘　　要：研究了以4-庚酮、5-壬酮和2,6-二甲基-4-庚酮为原料,通过烯醇化、氧化和亲核取代等反应,制备3-(2-甲基-3-呋喃硫基)-4-庚酮、4-(2-甲基-3-呋喃硫基)-5-壬酮和2,6-二甲基-3-(2-甲基-3-呋喃硫基)-4-庚酮3个香料化合物的方法。首先酮在碱性条件下与三甲基氯硅烷反应得到相应的烯醇硅醚,4-庚酮和5-壬酮形成烯醇硅醚产率均在80%以上,2,6-二甲基-4-庚酮形成烯醇硅醚产率略低,约70%。烯醇硅醚用间氯过氧苯甲酸氧化,得到α-羟基酮,产率均在85%左右。α-羟基酮与甲磺酰氯反应,得到相应的甲磺酸酯,然后在碱性条件下甲磺酸酯与2-甲基-3-呋喃硫醇反应生成α-(2-甲基-3-呋喃硫基)酮类香料化合物,产率在80%左右。最终产物通过~1HNMR,^(13)CNMR及MS进行了表征。Methods for synthesis of 3 - （ 2 - methyl - 3 - furyhhio） - 4 - heptanone, 4 - （ 2 - methyl - 3 - furylthio） - 5 - nonanone and 2,6 - dimethyl - 3 - （ 2 - methyl - 3 - furylthio） - 4 - heptanone, starting from 4 - heptanone, 5 - nonanone and 2,6 - dimethyl - 4 - heptanone respectively, through enolization, oxidation and nucleophilic substitution were studied. Firstly, silyl enol ethers were formed by reactions of corresponding ketones with chlorotrimethyl silane under alkaline condition. Yield of corresponding silyl enol ethers from 4 - heptanone and 5 -nonanone achieves 80% and higher, while yield of silyl enol ether from 2,6 -dimethyl - 4- heptanone aehieves 70%. The silyl enol ethers were oxidized by m - ehloroperbenzoie acid to form corresponding a - hydroxy ketones with a yield of about 85%. The α-hydroxy ketones were further reacted with methyl sulfonyl chloride to form corresponding methyl sulfonates, and then the methyl sulfonates were further reacted with 2 -methyl -3 -furanthiol under alkaline condition to obtain corresponding products, α-（2 -methyl-3 -furyhhio） ketones with a yield of about 80%. The products were characterized by 1HNMR, 13CNMR and MS.

关 键 词：肉味香料化合物 α-(2-甲基-3-呋喃硫基)酮 烯醇硅醚 氧化 

分 类 号：TQ655[化学工程—精细化工]