TY - JOUR

T1 - Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids

AU - Wang, Siqi

AU - Zonov, Yaroslav V

AU - Karpov, Victor M

AU - Luzina, Olga A

AU - Mezhenkova, Tatyana V

N1 - The authors are grateful to the Multi-Access Chemical Research Center of SB RAS for spectral and analytical measurements. Siqi Wang thanks the China Scholarship Council for its support.

PY - 2022/12/10

Y1 - 2022/12/10

N2 - 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-SbF5 mixture, or a FSO3H-SbF5 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 FSO3H-SbF5 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 α,β-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.

AB - 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-SbF5 mixture, or a FSO3H-SbF5 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 FSO3H-SbF5 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 α,β-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.

KW - Molecular Structure

KW - Ethanol

KW - Dicarboxylic Acids

KW - Carbon Monoxide

KW - carbonylation of alcohol

KW - polyfluorinated compound

KW - superacid

KW - antimony pentafluoride

KW - fluorosulfonic acid

KW - trifluoromethanesulfonic acid

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85144555755&origin=inward&txGid=b93ad76738ab588323fc80ada5da449a

UR - https://www.mendeley.com/catalogue/26f142bd-21b0-33a2-9c79-f3a0992f77ca/

U2 - 10.3390/molecules27248757

DO - 10.3390/molecules27248757

M3 - Article

C2 - 36557890

VL - 27

SP - 8757

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 24

ER -