(3R,4S)-(3-乙烯基-4-叔丁氧羰基甲基)-哌啶的合成  

STUDY ON THE SYNTHESIS OF (3R,4S)-3-VINYL-4-TERT-BUTOXYCARBONYLMETHYL-PIPERIDINE

作　　者：王佩[1] 黄龙江[1] 

机构地区：[1]青岛科技大学化工学院,山东青岛266042

出　　处：《精细石油化工》2016年第6期39-44,共6页Speciality Petrochemicals

摘　　要：以奎宁盐酸盐为原料,经中和反应、羟基氧化反应、羰基邻位断裂/亲核开环串联反应合成(3R,4S)-(3-乙烯基-4-叔丁氧羰基甲基)-哌啶。并对羟基氧化以及羰基邻位断键/亲核开环等关键步骤的工艺条件进行了优化,较佳的工艺条件为:羟基氧化选用二苯甲酮作为氧化剂,叔丁醇钾作为催化剂,干燥的甲苯为溶剂,反应收率为99.0%;羰基邻位断键/亲核开环反应:在氧气氛围下,2.4倍量底物摩尔量的叔丁醇钾为碱,四氢呋喃/叔丁醇(体积比)=2∶1为溶剂,反应收率为83.0%。目标产品的总收率达到了75.2%。（3R,4S）-3-vinyl-4-tert-butoxycarbonylmethyl-piperidine was prepared from quinine hydrochloride by the reaction of neutralization with sodium hydroxide,oxidation of hydroxyl group and ＂one-pot＂breaking C—C bond ofαposition of carbonyl group and nucleophilic ring opening.The reaction conditions of two key steps were optimized.For oxidation of hydroxyl group：benzophenone as the oxidant,potassium t-butoxide as a catalyst,dry toluene as solvent,the yield is 99.0%.For＂one-pot＂breaking C—C bond ofαposition of carbonyl group and nucleophilic ring opening：in the presence of O_2,substrate＇s 2.4equiv potassiumt-butoxide as base,V（THF）/V（t-BuOH）=2∶1as solvent,the yield is 83.0%.The total yield of the target product is 75.2%.

关 键 词：(3R 4S)-(3-乙烯基-4-乙酸叔丁酯基)-哌啶 奎宁 合成 

分 类 号：TQ253.2[化学工程—有机化工]