钛酸异丙酯催化脱氢芳樟醇合成柠檬醛

doi:10.16085/j.issn.1000-6613.2016.04.038

化工进展 ›› 2016, Vol. 35 ›› Issue (04): 1203-1207.DOI: 10.16085/j.issn.1000-6613.2016.04.038

钛酸异丙酯催化脱氢芳樟醇合成柠檬醛

赵宁波, 朱志庆

华东理工大学化工学院, 上海 200237

收稿日期:2015-09-09 修回日期:2015-09-21 出版日期:2016-04-05 发布日期:2016-04-05
通讯作者: 朱志庆,教授,主要从事有机合成与催化剂的研究.E-mail:zhuzq@ecust.edu.cn.
作者简介:赵宁波(1990-),男,硕士研究生.

Synthesis of citral from dehydrolinalool catalyzed by titanium isopropylate

ZHAO Ningbo, ZHU Zhiqing

School of Chemical Engineering, East China University of Science & Technology, Shanghai 200237, China

Received:2015-09-09 Revised:2015-09-21 Online:2016-04-05 Published:2016-04-05

摘要/Abstract

摘要： 以钛酸异丙酯为主催化剂,氯化亚铜为助催化剂,在氮气保护和有机酸的存在下,研究了脱氢芳樟醇经迈耶－舒斯特重排反应合成柠檬醛.优化的反应条件如下:n(钛酸异丙酯):n(氯化亚铜)=4:1,催化剂(钛酸异丙酯+氯化亚铜)和对甲基苯甲酸的用量分别为原料脱氢芳樟醇质量的3.5%和10%,在110℃下反应3h,得到脱氢芳樟醇的转化率为98.8%,生成柠檬醛的收率为88.4%.采用水蒸气蒸馏的方法分离反应液,得到纯度≥97%的柠檬醛,采用FTIR对产物进行表征,确定了产品柠檬醛中所含有的主要杂质.最后,探讨了脱氢芳樟醇合成柠檬醛的反应机理.

关键词: 钛酸异丙酯, 氯化亚铜, 脱氢芳樟醇, 柠檬醛

Abstract: With titanium isopropylate as the primary catalyst and cuprous chloride as promoter, citral was synthesized from dehydrolinalool through Meyer-Schuster rearrangement in the presence of organic acid under nitrogen atmosphere. The optimized conditions were as follow:n(titanium isopropylate):n(cuprous chloride) was 4:1, the dosage of catalyst (titanium isopropylate + cuprous chloride) was 3.5% of dehydrolinalool, the amount of 4-methylbenzoic acid was 10% of dehydrolinalool, the reaction was operated at 110℃ for 3h. The conversion of dehydrolinalool was 98.8% and the yield of citral was 88.4%. Citral with purity of ≥97% was separated from reaction mixtures by steam distillation. The product was characterized by means of FTIR and the main impurities in the citral were also identified . The synthesis mechanism of citral from dehydrolinalool was discussed.

Key words: titanium isopropylate, cuprous chloride, dehydrolinalool, citral

中图分类号:

TQ651⁺.1

赵宁波, 朱志庆. 钛酸异丙酯催化脱氢芳樟醇合成柠檬醛[J]. 化工进展, 2016, 35(04): 1203-1207.

ZHAO Ningbo, ZHU Zhiqing. Synthesis of citral from dehydrolinalool catalyzed by titanium isopropylate[J]. Chemical Industry and Engineering Progree, 2016, 35(04): 1203-1207.

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钛酸异丙酯催化脱氢芳樟醇合成柠檬醛

Synthesis of citral from dehydrolinalool catalyzed by titanium isopropylate

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