钛酸异丙酯催化脱氢芳樟醇合成柠檬醛.pdf

化工进展
2016年第35卷第4期
CHEMICAL INDUSTRY AND ENGINEERING PROGRESS
1203
cec se dde
研究开发
钛酸异丙酯催化脱氢芳樟醇合成楟檬醛
赵宁波,朱志庆
(华东理工大学化工学院,上海200237)
摘要:以钛酸异丙酯为主催化剂,氟化亚铜为助催化剂,在気气保护和有机酸的存在下,研究了脱氩芳樟醇经
迈耶一舒斯特重排反应合成柠檬醛。优化的反应条件如下:m(钛酸异丙酯):(氯化亚铜)4:1,催化剂(钛酸异
丙酯+氟化亚铜)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
氲芳樟醇的转化率为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,得到纯度ン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,探讨了脱氩芳樟醇合成
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
中图分类号:TQ651.1
文献标志码:A
文章编号:1000-66131(2016)04-1203-05
DOI:10.16085/jsn.,1000-6613.2016.04.038
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)
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 cupro
chloride ) was 3.5% of dehydrolinalool the amount of 4-methylbenzoic acid was 10% of
dehydrolinalool, the reaction was operated at 110 C 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
柠檬醛具有浓郁的柠檬香味,可用于生产柑制。柠檬醛也可以通过不同的化学方法合成,其中
橋香味食品香料直接用于饮料和食品加工。柠檬由脱氢芳樟醇在催化剂的作用下,通过迈耶-舒斯特
醛作为最重要的开链单萜之一,是一种重要的精细( Meyer- Schuster)重排反应,直接合成柠檬醛,具
化工中间体,可用于合成异胡薄荷醇、羟基香茅有原料易从石油化工制得、反应条件相对温和的优
醛和紫罗兰酮,还可转化成生产维生素E、维生点,适合于规模化大生产。脱氢芳樟醇是以石油化
素A、异植物醇等的重要起始原料。天然柠檬醛
存在于山苍子油等许多植物精油中,从中可以提取
收稿日期:2015-09-09;修改稿月期:2015-09-21。
第一作者:赵宁波(1990-),男,硕士研究生。联系人:朱志庆,教
生产柠檬醛,但是产量和规模受到原料资源的限
投,主要从事有机合成与催化剂的研究。E-mailzhuzq@ecust.edu.cn