3,3-二甲基-1-丁烯的合成工艺研究

摘要

以叔丁醇为原料,优化了其与浓盐酸氯代合成叔丁基氯的反应,采用CaCl₂ 氯化盐助催化体系使反应收率提高到95%,产品质量分数为99%;3,3-二甲基-1-丁烯合成的关键步骤是叔丁基氯与乙烯反应制备3,3-二甲基-1-氯丁烷,探讨了催化剂用量、反应温度对反应收率的影响.反应以无水三氯化铝为催化剂,用量为n(AlCl₃):n[(CH₃)₃CCl]=0.018:1,反应温度为-17~-20 ℃时,产物3,3-二甲基-1-氯丁烷的收率可达80%;最后由3,3-二甲基-1-氯丁烷脱氯化氢制备3,3-二甲基-1-丁烯.考察了不同溶剂对反应收率的影响,以聚乙二醇-400为溶剂,无需加入相转移催化剂,收率可达88.5%,3,3-二甲基-1-丁烯的质量分数为可达95%以上.

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	李宁
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关键词：叔丁醇； 3,3-二甲基-1-氯丁烷； 3,3-二甲基-1-丁烯；精细化工中间体

Abstract：

The tertiary butyl alcohol was chosen as a raw material to prepare 3,3-dimethyl-1-butene. The reaction conditions of tertiary butyl alcohol and concentrated hydrochloric acid were optimized. The yield was increased to 95% and the purity of product could reach 99% using 32% hydrochloric acid and CaCl₂ co-catalyst system. Then, the key-step of this method was the preparation of 1-chloro-3,3-dimethylbutane using tert-butyl chloride and ethylene. The influences of catalyst dosage and reaction temperature on the yield of product were investigated. The yield can be up to 85% when using anhydrous AlCl₃ as catalyst with catalyst dosage of n(AlCl₃):n((CH₃)₃CCl)=0.018:1 and the reaction temperature was -20—-17 ℃. Finally, the 3,3-dimethyl-1-butene was obtained by dehydrochlorination of 1-chloro-3,3-dimethylbutane. The impact of different solvents on the yield was studied. The results show that the best solvent is polyethylene glycol-400, which can improve the purity of product to more than 95% and the yield up to 88.5% without phase transfer catalyst.

Keywords： tertiary butyl alcohol； 3,3-dimethyl-1-butene； 1-chloro-3,3-dimethylbutane； fine chemical intermediates

Received 2013-08-22;

Corresponding Authors: 李宁,E-mail: liyining@163.com. Email: liyining@163.com

About author: 李宁(1989-),男,研究领域为有机化学.

引用本文:

李宁, 唐向阳, 齐欣.3,3-二甲基-1-丁烯的合成工艺研究[J]. 化学工业与工程, 2015,32(6): 22-25,73

Li Ning, Tang Xiangyang, Qi Xin.Synthesis of 3,3-Dimethyl-1-Butene[J]. Chemcial Industry and Engineering, 2015,32(6): 22-25,73

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