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Updated: May 23, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
PCl3 or PCl3/SnCl4-promoted fluoroalkylthiolation of arenes with fluoroalkanesulfinyl chlorides
Tian-Cheng Zhong1, Min Jiang2, Jin-Tao Liu1,2
1The Education Ministry Key Lab of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai 200234, China.
Abstract:
A practical method for the fluoroalkylthiolation of arenes has been developed using fluoroalkanesulfinyl chlorides as fluoroalkylthiolating reagents and PCl3 or PCl3/SnCl4 as the promoter. A series of fluoroalkylthiolated arenes were obtained in moderate to high yields under mild conditions. The reaction of highly activated arenes worked smoothly in the presence of PCl3 at room temperature, while less nucleophilic arenes required cooperative promotion of PCl3 and SnCl4 at higher temperature. Based on 19F NMR monitoring of the reaction systems, two plausible reaction pathways were proposed, involving either a fluoroalkylsulfinylated intermediate or a fluoroalkanesulfenyl chloride species.
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