基于复合氯化剂CuCl2·5/3NaCl·5/2Al2O3的1-氯-2-芳基乙炔的合成

doi:10.6023/cjoc201403036

有机化学 ›› 2014, Vol. 34 ›› Issue (10): 2099-2105.DOI: 10.6023/cjoc201403036 上一篇下一篇

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基于复合氯化剂CuCl₂·5/3NaCl·5/2Al₂O₃的1-氯-2-芳基乙炔的合成

刘淑琴, 赵子剑, 肖竞, 石磊, 冯伶俐, 彭志鸿, 安德烈

化学生物传感与计量学国家重点实验室湖南大学化学化工学院长沙 410082

收稿日期:2014-03-15 修回日期:2014-05-06 发布日期:2014-06-03
通讯作者: 彭志鸿, 安德烈 E-mail:deliean@hnu.edu.cn
基金资助:
国家自然科学基金（No. 21072052）和湖南省科技计划（No. 2011 WK4007）资助项目.

Synthesis of 1-Chloro-2-aryl Ethyne Using CuCl₂·5/3NaCl·5/2Al₂O₃ as Composite Chlorinating Agent

Liu Shuqin, Zhao Zijian, Xiao Jing, Shi Lei, Feng Lingli, Peng Zhihong, An Delie

State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082

Received:2014-03-15 Revised:2014-05-06 Published:2014-06-03
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21072052) and the Hunan Provincial Science and Technology Department Program (No. 2011 WK4007).

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1. 基于复合氯化剂CuCl₂·5/3NaCl·5/2Al₂O₃的1-氯-2-芳基乙炔的合成.PDF(3275KB)

摘要/Abstract

直接使用CuCl₂氯化芳基乙炔的反应通常存在着选择性差（有取代氯化和多种加成氯化的产物生成）、副产物多和分离困难等问题. 描述了一种复合氯化剂（CuCl₂·无机盐·载体）的制备以及基于该氯化剂取代氯化芳基乙炔的有效方法. 首先通过一系列对比实验获得了CuCl₂、载体和无机盐添加物的最佳配比. 在此基础上考察了溶剂、复合氯化剂用量、反应温度诸因素对取代氯化反应的影响，提出了最佳反应条件：复合氯化剂为CuCl₂·5/3NaCl·5/2Al₂O₃，芳基乙炔与氯化剂的物质的量比为1∶3，溶剂为CH₂Cl₂，反应温度为35 ℃. 在优化条件下，高产率（72%～99%）地合成了一系列1-氯- 2-芳基乙炔目标产物1a～1n，并对这些化合物进行了表征. 该方法反应条件温和、产率高、选择性好，并且适用于芳环上带有各种基团的底物.

关键词: 复合氯化剂, 芳基乙炔, 取代氯化, 1-氯-2-芳基乙炔

An effective protocol for substitution chlorination was accomplished using a new composite chlorinating agent from CuCl₂, inorganic salt and carrier. The most appropriate ratio of each individual component of composite chlorinating agent was determined by comparative experiments. The optimal synthetic conditions for 1-chloro-2-aryl ethyne were obtained by the investigation of various factors, including solvents, the amount of composite chlorinating agents and reaction temperature. The mild and simple method allowed the formation of 1-chloro-2-aryl ethyne in up to 99% yields and showed good selectivities. Various substrates bearing inert or sensitive groups were tolerable for the present preparation. A plausible mechanism for the reaction was also proposed.

Key words: composite chlorinating agent, aryl ethyne, substitution chlorination, 1-chloro-2-aryl ethyne

引用此文

刘淑琴, 赵子剑, 肖竞, 石磊, 冯伶俐, 彭志鸿, 安德烈. 基于复合氯化剂CuCl₂·5/3NaCl·5/2Al₂O₃的1-氯-2-芳基乙炔的合成[J]. 有机化学, 2014, 34(10): 2099-2105.

Liu Shuqin, Zhao Zijian, Xiao Jing, Shi Lei, Feng Lingli, Peng Zhihong, An Delie. Synthesis of 1-Chloro-2-aryl Ethyne Using CuCl₂·5/3NaCl·5/2Al₂O₃ as Composite Chlorinating Agent[J]. Chin. J. Org. Chem., 2014, 34(10): 2099-2105.

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基于复合氯化剂CuCl₂·5/3NaCl·5/2Al₂O₃的1-氯-2-芳基乙炔的合成

Synthesis of 1-Chloro-2-aryl Ethyne Using CuCl₂·5/3NaCl·5/2Al₂O₃ as Composite Chlorinating Agent

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