The aliphatic ring-opening and SNAr substitution in the reactions of perfluorobenzocycloalkenones with K2CO3 in water and methanol

Yaroslav V. Zonov, Siqi Wang, Victor M. Karpov, Tatyana V. Mezhenkova

Research output: Contribution to journalArticlepeer-review

Abstract

In the reactions with aqueous K2CO3, perfluorinated benzocyclobuten-1-one, 3-R-indan-1-ones and 4-R-tetralin-1-ones (R = F, C2F5) undergo selective cleavage of the СO–С(Ar) bond to yield (2,3,4,5-tetrafluorophenyl)perfluoroalkanoic acids after acidification of the reaction mixture; benzocyclobuten-1-ones and indan-1-ones bearing perfluoroalkyl or perfluorophenyl group at C(2) react predominantly or exclusively with cleavage of the СO–С(2) bond to form 2-substituted tetrafluorobenzoic acids; 3,3-diethylindan-1-one gives 5- and 7-hydroxy derivatives as the only products, whereas for 3-ethylindan-1-one SNAr substitution of fluorine atoms and the five-membered ring-opening are competitive processes; benzocyclobutene-1,2-dione, indan-1,3-dione and tetralin-1,4-dione undergo cleavage of the СO–С(Ar) bond to yield ω-(2,3,4,5-tetrafluorophenyl)-ω-oxoperfluoroalkanoic acids, but only the former reacts selectively, in the other diketones, the СO–С(2) bond cleavage or/and nucleophilic substitution of fluorine atoms also occurs. Perfluobenzocyclobuten-1-one and -1,2-dione react with K2CO3 in methanol similar to their transformation in the aqueous medium to form methyl (2,3,4,5-tetrafluorophenyl)difluоroacetate and - oxoacetate, respectively, whereas perfluoroindan-1-one with K2CO3 in methanol gives 5-methoxyperfluоroindan-1-one.

Original languageEnglish
Article number109851
JournalJournal of Fluorine Chemistry
Volume249
DOIs
Publication statusPublished - Sep 2021

Keywords

  • Benzocyclobutenone
  • Carboxylic acid
  • Indanone
  • Ketone
  • Perfluorinated
  • Ring-opening
  • Tetralon

OECD FOS+WOS

  • 1.05 EARTH AND RELATED ENVIRONMENTAL SCIENCES
  • 1.06 BIOLOGICAL SCIENCES
  • 1.04 CHEMICAL SCIENCES

Fingerprint

Dive into the research topics of 'The aliphatic ring-opening and S<sub>N</sub>Ar substitution in the reactions of perfluorobenzocycloalkenones with K<sub>2</sub>CO<sub>3</sub> in water and methanol'. Together they form a unique fingerprint.

Cite this