Research progress in the synthesis of α-hydroxycyclohexyl phenyl ketone

doi:10.16085/j.issn.1000-6613.2019-0619

Abstract

Abstract:

α-hydroxycyclohexyl phenyl ketone (Irgacure184) is a type of high-efficiency photoinitiator, which is widely applied in electronics, coatings, printing, etc. This paper classifies its synthesis methods according to different starting materials and summarizes the characteristics of each method. Meanwhile, this paper mainly introduces the process of using cyclohexyl phenyl ketone as raw material and other routes to synthesize α-hydroxycyclohexyl phenyl ketone. At present, the Friedel-Crafts acylation method for synthesizing α-hydroxycyclohexyl phenyl ketone is most commonly used. However, because of the wastes and the strong toxicity, this method does not meet the requirements of green chemistry and will gradually be eliminated. Among all the synthesis routes, using the Grignard reaction to obtain α-hydroxycyclohexyl phenyl ketone is expected to be one of the most considerable directions owing to its high yield and environmental benign nature. At the end, the trend of researches on synthesizing α-hydroxycyclohexyl phenyl ketone is pointed out.

Key words: α-hydroxycyclohexyl phenyl ketone, Friedel-Crafts acylation, Grignard reaction

摘要：

α-羟基环己基苯基甲酮（光引发剂184）是一种高效光引发剂，因其引发效率高、稳定性好、耐黄变等优势，在电子、涂料、印刷等领域得到广泛的应用。本文根据起始原料不同对α-羟基环己基苯基甲酮的合成方法进行分类，并归纳了不同合成方法的特点。重点介绍了以环己基苯基甲酮为中间体的合成工艺以及其他合成α-羟基环己基苯基甲酮的工艺路线。目前，工业上最常用的Friedel-Crafts酰基化法合成光引发剂184的工艺路线，因为产生的三废多且有毒有害，不符合绿色化工的要求，而将逐渐被淘汰。以格氏反应法合成环己基苯基甲酮继而再合成α-羟基环己基苯基甲酮的工艺路线，因其收率高、污染少等优点而有望成为合成α-羟基环己基苯基甲酮的重要发展方向之一。最后，指出了α-羟基环己基苯基甲酮合成工艺研究的趋势。

关键词: α-羟基环己基苯基甲酮, Friedel-Crafts酰基化, 格氏反应

CLC Number:

TQ072

Minjia WANG, Ze XU, Jiancheng RUAN, Xinzhi CHEN. Research progress in the synthesis of α-hydroxycyclohexyl phenyl ketone[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 365-371.

王敏嘉, 徐泽, 阮建成, 陈新志. α-羟基环己基苯基甲酮合成工艺研究进展[J]. 化工进展, 2020, 39(1): 365-371.

Figures/Tables 14

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工艺路线	主要原料	催化剂	单元反应	特点
卤化水解法	环己基苯基甲酮、卤素、氢氧化钠	—	卤化、水解	收率高、反应条件温和、三废多
催化氧化法	环己基苯基甲酮	H₂O₂/TBAB	催化氧化	工艺路线短、收率高、操作危险性大
芐位氧化法	1-芐基环己醇	PTC/可见光	芐位催化氧化反应	氧化剂腐蚀性强、污染较大且成本较高
醇氧化法	α-羟基-苯基甲基环己醇	Br₂/CuCl/可见光	氧化反应	收率较高、催化剂腐蚀性较强
亲核加成法	三甲基甲硅烷氧基化合物	I₂/LDA	亲核加成反应、水解	收率较高、硅烷回收困难、反应活性不强、反应时间较长
Favorskii重排反应法	2-羟基-2-苯基-环庚酮	BF₃·OEt₂/ Pb(NO₃)₂	Favorskii重排反应	收率较低、分离提纯较困难
其他方法	卤化苄、硫醚/1-羟基-环己基甲酸、苯基锂/环己酮、苯甲酰氯	—	—	工艺比较复杂、产率低、分离提纯较困难、原料成本较高

工艺路线	主要原料	催化剂	单元反应	特点
卤化水解法	环己基苯基甲酮、卤素、氢氧化钠	—	卤化、水解	收率高、反应条件温和、三废多
催化氧化法	环己基苯基甲酮	H₂O₂/TBAB	催化氧化	工艺路线短、收率高、操作危险性大
芐位氧化法	1-芐基环己醇	PTC/可见光	芐位催化氧化反应	氧化剂腐蚀性强、污染较大且成本较高
醇氧化法	α-羟基-苯基甲基环己醇	Br₂/CuCl/可见光	氧化反应	收率较高、催化剂腐蚀性较强
亲核加成法	三甲基甲硅烷氧基化合物	I₂/LDA	亲核加成反应、水解	收率较高、硅烷回收困难、反应活性不强、反应时间较长
Favorskii重排反应法	2-羟基-2-苯基-环庚酮	BF₃·OEt₂/ Pb(NO₃)₂	Favorskii重排反应	收率较低、分离提纯较困难
其他方法	卤化苄、硫醚/1-羟基-环己基甲酸、苯基锂/环己酮、苯甲酰氯	—	—	工艺比较复杂、产率低、分离提纯较困难、原料成本较高