A facile and efficient synthesis of new fluoroalkylsulfonates and the corresponding tetrabutylammonium salts. Issue 35 (29th August 2019)

• Record Type: Journal Article
• Authors: Mu, Youbing; Wan, Xiaobo
• Is Part Of: Tetrahedron letters. Volume 60:Issue 35(2019)
• Publication Date: 2019-08-29
• Subjects: Grignard reagents -- Methyl 2, 2-difluoro-2-(fluorosulfonyl)acetate -- Fluoroalkylsulfonate -- Quaternary ammonium sulfonate compounds; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2019.150966
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: New fluoroalkylsulfonates were synthesized by Grignard addition reaction. The sulfonyl group helps to stabilize the tetrahedron intermediate to avoid side reactions. The hydration behavior of fluoroalkylsulfonate was studied. Tetra- n -butylammonium fluoroalkylsulfonates were easily prepared quantitatively. Abstract: A useful synthetic methodology towards new fluoroalkylsulfonates was developed. Grignard addition to an inexpensive and commercially available fluorine-containing ester, methyl 2, 2-difluoro-2-(fluorosulfonyl)acetate (1 ) gave the mono-adduct (2 ) as the only product in high yield. The scope and limitation of this method were thoroughly investigated and it was found that it works for most Grignard reagents except electron-poor ones. Interestingly, the resulting fluoroalkylsulfonates exhibit substituent-dependent hydration behavior due to the presence of carbonyl group in these compounds. Converting the fluoroalkylsulfonate to the acid form and then neutralizing it with tetra- n -butylammonium hydroxide gave the corresponding tetra- n -butylammonium salts, which shows good solubility in common organic solvents, some of which might be suitable for copolymerization with other hydrophobic monomers.