Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids

• Published in: Molecules (Basel, Switzerland) Vol. 27; no. 24; p. 8757
• Main Authors: Wang, Siqi, Zonov, Yaroslav V, Karpov, Victor M, Luzina, Olga A, Mezhenkova, Tatyana V
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 01.12.2022; MDPI
• Subjects: Acids; Alcohol; Alcohols; Alkylbenzenes; Antimony fluorides; antimony pentafluoride; Atmospheric pressure; Carbon Monoxide; carbonylation of alcohol; Carbonyls; Carboxylic acids; Dicarboxylic Acids; Diols; Equilibrium; Ethanol; Fluorides; Fluorine; fluorosulfonic acid; Glycols; Hydrolysis; Lactones; Mixtures; Molecular Structure; Organic acids; polyfluorinated compound; superacid; trifluoromethanesulfonic acid; Water treatment; carbonylation of alcohol; polyfluorinated compound; antimony pentafluoride; fluorosulfonic acid; trifluoromethanesulfonic acid; superacid
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27248757

We describe the carbonylation of a series of mono and dihydroxy derivatives of polyfluorinated alkylbenzenes and benzocycloalkenes with OH groups at benzylic positions using carbon monoxide in the presence of a superacid (TfOH, a TfOH-SbF mixture, or a FSO H-SbF mixture). It was shown that the superacid-catalyzed addition of CO to various primary and secondary polyfluorinated alcohols and diols gives the corresponding mono- and dicarboxylic acids or lactones. The efficiency of various superacids depending on alcohol structure was evaluated, and FSO H-SbF yielded the best results in most transformations. The addition of CO to secondary 1-arylalkan-1-ols containing vicinal fluorine atoms was found to be accompanied by elimination of HF with the formation of -unsaturated aryl-carboxylic acids. In contrast to primary and secondary alcohols, conversion of tertiary perfluoro-1,1-diarylalkan-1-ols into carbonylation products is not complete, and the resulting carboxylic acids are easily decarboxylated after water treatment of the reaction mixture.