Solvent-Free Friedel-Crafts Acylation of Fluorobenzene Catalyzed by Trifluoromethanesulfonic Acid and Rare Earth Triflates

doi:10.6023/cjoc201305049

Chin. J. Org. Chem. ›› 2013, Vol. 33 ›› Issue (12): 2572-2577.DOI: 10.6023/cjoc201305049 Previous Articles Next Articles

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无溶剂下三氟甲磺酸及稀土盐催化氟苯的傅克酰基化反应的研究

贾红燕, 谢作松, 郭耘, 郭杨龙, 王艳芹, 卢冠忠

华东理工大学工业催化研究所上海 200237

收稿日期:2013-05-30 修回日期:2013-07-21 发布日期:2013-08-12
通讯作者: 卢冠忠 E-mail:gzhlu@ecust.edu.cn
基金资助:
国家重点基础研究发展计划(973计划，No. 2010CB732300)资助项目.

Solvent-Free Friedel-Crafts Acylation of Fluorobenzene Catalyzed by Trifluoromethanesulfonic Acid and Rare Earth Triflates

Jia Hongyan, Xie Zuosong, Guo Yun, Guo Yanglong, Wang Yanqin, Lu Guanzhong

Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237

Received:2013-05-30 Revised:2013-07-21 Published:2013-08-12
Supported by:
Project supported by the National Basic Research Program (973 Program, No. 2010CB732300).

1. Solvent-Free Friedel-Crafts Acylation of Fluorobenzene Catalyzed by Trifluoromethanesulfonic Acid and Rare Earth Triflates.PDF(377KB)

Abstract

Solvent-free Friedel-Crafts acylation of fluorobenzene with benzoyl chloride was investigated over the trifluoromethanesulfonic acid (TfOH) and rare earth triflate (Re(OTf)₃) composite catalyst. The results showed that the presence of Re(OTf)₃ leads to the decrease in a half amount of TfOH catalyst, and there is a synergistic effect between TfOH and Re(OTf)₃ in this composite catalyst. For the solvent-free acylation of fluorobenzene with benzoyl chloride, the catalytic activities of 11 kinds of rare earth elements Re(OTf)₃ were tested, and it was found that among all Re(OTf)₃ compounds La(OTf)₃ exhibits the best catalytic performance and it can be repeatedly used. After the acylation of fluorobenzene with benzoyl chloride over the La(OTf)₃ and TfOH catalyst at 140 ℃ for 4 h, the selectivity and yield to para-product fluorobenzophenone reach up to 99% and 87%, respectively. For the acylation of different benzene derivatives with benzoyl chloride over the TfOH and Re(OTf)₃ catalyst, the promoting catalysis of different elements Re(OTf)₃ is different, for instance, for the acylation of dimethylbenzene, Ce(OTf)₃ exhibits the best catalytic performance among the tested Re(OTf)₃ promoters.

Key words: Trifluoromethanesulfonic acid and rare earth triflate, Fuorobenzene, Benzoyl chloride, Friedel-Crafts acylation, Composite catalyst system

Cite this article

Jia Hongyan, Xie Zuosong, Guo Yun, Guo Yanglong, Wang Yanqin, Lu Guanzhong. Solvent-Free Friedel-Crafts Acylation of Fluorobenzene Catalyzed by Trifluoromethanesulfonic Acid and Rare Earth Triflates[J]. Chin. J. Org. Chem., 2013, 33(12): 2572-2577.

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无溶剂下三氟甲磺酸及稀土盐催化氟苯的傅克酰基化反应的研究

Solvent-Free Friedel-Crafts Acylation of Fluorobenzene Catalyzed by Trifluoromethanesulfonic Acid and Rare Earth Triflates

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