Research output: Contribution to journal › Article › peer-review
The aliphatic ring-opening and SNAr substitution in the reactions of perfluorobenzocycloalkenones with K2CO3 in water and methanol. / Zonov, Yaroslav V.; Wang, Siqi; Karpov, Victor M. et al.
In: Journal of Fluorine Chemistry, Vol. 249, 109851, 09.2021.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - The aliphatic ring-opening and SNAr substitution in the reactions of perfluorobenzocycloalkenones with K2CO3 in water and methanol
AU - Zonov, Yaroslav V.
AU - Wang, Siqi
AU - Karpov, Victor M.
AU - Mezhenkova, Tatyana V.
N1 - Funding Information: 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 support and funding. Publisher Copyright: © 2021 Elsevier B.V. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2021/9
Y1 - 2021/9
N2 - 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.
AB - 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.
KW - Benzocyclobutenone
KW - Carboxylic acid
KW - Indanone
KW - Ketone
KW - Perfluorinated
KW - Ring-opening
KW - Tetralon
UR - http://www.scopus.com/inward/record.url?scp=85111027898&partnerID=8YFLogxK
U2 - 10.1016/j.jfluchem.2021.109851
DO - 10.1016/j.jfluchem.2021.109851
M3 - Article
AN - SCOPUS:85111027898
VL - 249
JO - Journal of Fluorine Chemistry
JF - Journal of Fluorine Chemistry
SN - 0022-1139
M1 - 109851
ER -
ID: 29131500