1-[反式-4-(反式-4-正戊基环己基)环己基]乙炔制备的新方法  

New Synthetic Method of 1-(Trans-4-(trans-4-n-pentylcyclohexyl)-cyclohexyl)acetylene

作　　者：李建[1] 胡明刚[1] 杜渭松[1] 安忠维[1] 

机构地区：[1]西安近代化学研究所八部,西安710065

出　　处：《应用化学》2008年第3期313-316,共4页Chinese Journal of Applied Chemistry

基　　金：陕西省重大科技专项基金资助(2006kz03-G3)

摘　　要：以1-[反式-4-(反式-4-正戊基环己基)环己基]乙烯为原料,经溴加成、消除2个HB r分子,制备出1-[反式-4-(反式-4-正戊基环己基)环己基]乙炔,反应总收率为76.7%,色谱纯度达到96%,反应条件温和,简便易行。研究了消除反应条件对收率的影响。反应温度为80℃,反应2 h即可完成;反应时间延长至6 h,以51.5%的收率得到连二烯副产物。产物结构经MS、IR、NMR测试技术确认。对反应机理进行了推测,目标化合物中与炔键相连的环己烷碳上氢原子,在叔丁醇钾作用下发生迁移重排,生成热力学稳定的连二烯化合物。通过控制反应条件可以选择性地得到环己基乙炔或连二烯化合物,为环己基乙炔的制备提供了新方法。（Trans-4-（trans-4-n-pentylcyclohexyl） cyclohexyl）acetylene was synthesized with （trans-4-n-pentylcyclohexyl）-cyclohexyl ）ethylene as starting material via bromine addition, 1-（ trans-4- then two molecules of hydrogen bromide were eliminated. The overall yield was 76.7% with a chromatogram purity of 96%. This method is facile to practise and contains a few steps. The impact of elimination conditions on yield was studied. The reaction was finished within 2 h at 80 ℃, and a cumulative diene by-product turned to be main product when the reaction time was prolonged to 6 h with a yield of 51.5%. The structures of products were identified by IR, MS and NMR. The mechanism of the rearrangement was proposed, i.e. , the hydrogen migrated under the action of alkaline, which resulted in a thermodynamically stable cumulative diene by-product. A new path was provided to obtain cyclohexyl-substituted acetylene or cumulative diene selectively by controlling the reaction conditions.

关 键 词：环己基乙炔 连二烯 液晶中间体 合成 消除反应 

分 类 号：O621[理学—有机化学]