高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (8): 1686.doi: 10.7503/cjcu20140051

• 有机化学 • 上一篇    下一篇

对称桥头二取代金刚烷衍生物的合成

徐晓健, 郭建维(), 朱东雨, 钟星   

  1. 广东工业大学轻工化工学院, 广州 510006
  • 收稿日期:2014-01-16 出版日期:2014-08-10 发布日期:2014-07-04
  • 作者简介:联系人简介: 郭建维, 男, 博士, 教授, 博士生导师, 主要从事精细石油化工及多相催化研究. E-mail: doctorgjw@163.com
  • 基金资助:
    广东省高等学校重点技术创新项目(批准号: 2012KJCX0043)资助

Synthesis of Symmetrical Disubstituted Bridgehead Adamantane Derivatives

XU Xiaojian, GUO Jianwei*(), ZHU Dongyu, ZHONG Xing   

  1. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China
  • Received:2014-01-16 Online:2014-08-10 Published:2014-07-04
  • Contact: GUO Jianwei E-mail:doctorgjw@163.com
  • Supported by:
    Supported by the Key Program for Scientific and Technological Innovations of Higher Education Institutes in Guangdong Province of China (No. 2012KJCX0043).

摘要:

以易得的1-金刚烷甲酸为原料, 合成了一系列对称桥头二取代金刚烷衍生物. 由1-金刚烷甲酸经Koch-Haaf羰基化反应得到1,3-金刚烷二甲酸(1); 化合物1经还原得到1,3-金刚烷二甲醇(2); 化合物2在HBr-ZnBr2体系中经溴代反应得1,3-二(溴甲基)金刚烷(3); 同时经Apple-Lee反应将化合物2转化得到1,3-二(氯甲基)金刚烷(4). 采用红外光谱和核磁共振氢谱等手段表征了产物的结构, 提出了可能的反应机理, 并对合成条件进行了优化.

关键词: 金刚烷, 1, 3-金刚烷二甲酸, 1, 3-金刚烷二甲醇, 1, 3-二(溴甲基)金刚烷, 1, 3-二(氯甲基)金刚烷

Abstract:

The symmetric bridge disubstituted adamantane derivatives are the key raw materials or interme-diates for preparing multisubstituted adamantane derivatives with admantane as the core. With 1-adamantane carboxylic acid that is more efficient and economical as an initial reactant, a series of synthesis technologies of symmetrical disubstituted bridgehead adamantane derivatives which have significant applications, were studied in this work. Those synthesis technologies include the following: 1,3-adamantane dicarboxylic acid(1) was synthesized by 1-adamantane carboxylic acid through Koch-Haaf carbonylation; compound 1 was reduced to get 1,3-adamantane dimethanol(2); compound 2 reacted by bromination in HBr-ZnBr2 system to afford 1,3-dibromomethyl adamantane(3). Meanwhile, compound 2 converted to 1,3-dichloromethyl adamantane(4) through Apple-Lee reaction. The structures of prepared products were confirmed by IR spectra and 1H NMR spectroscopy. The possible reaction mechanism was proposed, and the synthesis conditions were discussed and optimized for each technology respectively.

Key words: Adamantane, 1, 3-Adamantane dicarboxylic acid, 1, 3-Adamantane dimethanol, 1, 3-Dibromo-methyl adamantane, 1, 3-Dichloromethyl adamantane

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