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Electrochemical Carboxylation of Vinyl Compounds

Research Project

Project/Area Number 63550608
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 工業物理化学
Research InstitutionThe University of Tokushima

Principal Investigator

KUNUGI Akira  The University of Tokushima, Faculty of Engineering, Professor, 工学部, 教授 (20047062)

Co-Investigator(Kenkyū-buntansha) YASUZAWA Mikito  The University of Tokushima, Faculty of Engineering, Assistant, 工学部, 助手 (70210250)
Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1989: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1988: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsOrganosulfur Compound / Vinyl Sulfoxide / Vinyl Sulfone / Electroreductive Desulfurization / Electrochemical Carboxylation / Fixation of Carbon Dioxide
Research Abstract

Carbon dioxide is well known to be a useful reagent for the trapping of anionic species in solution resulting in the formation of carboxylated products. For example, the electrolytic reduction of activated olefins such as 1-cyanostyrene in the presence of carbon dioxide gives the corresponding saturated compounds with the carboxyl group. With alpha, beta-unsaturated sulfoxides and sulfones, on the other hand, the substitution of sulfinyl or sulfonyl group by carbon dioxide will be expected to occur to yield the corresponding acrylic acid derivatives, in contrast to the above example.
The present work deals with the electrochemical carboxylation of alpha, beta-unsaturated sulfoxides and sulfones with carbon dioxide in nonaqueous media. These results are shown below :
(1) The electro-carboxylation of beta-methylsulfenyl-beta-methylsulfinylstyrene leads to alpha- (methylsulfenyl) cinnamic acid and beta-methylsulfenylstyrene.
This electro-carboxylation is characterized as substitution of the methylsulfinyl group by carbon dioxide.
(2) The electro-carboxylation of 1-methylthio-1-p-tolylsulfony1-2-arylethenes gives 3-arylpropenoic acids, indicating that the elimination of both methylthio and p-tolylsulphonyl groups happens.
(3) In the electroreductive desulfurization and carboxylation of beta, beta-bis (methylsulfonyl) styrene, the selective cleavage of one carbon-sulfur bond takes place to afford beta-methylsulfonylstyrene in the presence of an efficient proton donor, but the corresponding carboxylated product is not obtained in the presence of carbon dioxide.
(4) The electrochemical reduction of alpha, beta-bis (methylsulfonyl) styrene in nonaqueous media leads to beta-methylsulfonylstyrene. This is contrary to experience with above compounds, i. e., this electro-reduction brings about the elimination of the methylsulfonyl group at the alpha-position rather than the beta-position. The electro-carboxylation of this compound gives beta-methylsulfonyl-alpha-phenylacrylic acid.

Report

(3 results)
  • 1990 Final Research Report Summary
  • 1989 Annual Research Report
  • 1988 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] 椚 章: "β、βービス(メチルスルホニル)スチレンのアセトニトリル/水銀電極系における電解還元反応" Chem.Express. 4. 189-192 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Akira Kunugi: "Electroreductive carboxylation of 1ーmethylthioー1ーpーtolylsulfonyl 2ーarylethenes in N,Nーdimethylformamide" Denki Kagaku. 58. 264-265 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Akira Kunugi: "Electroreductive desulfurization and Carboxylation of α,βーbis(methylsulfonyl)styrene in nonaqueous media" Denki Kagaku.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Akira Kunugi: "Electrochemical carboxylation of βーmethysulphenylーβーmethylsulphinylstyrene in N,Nーdimethylformamide containing carbon dioxide" Electrochim.Acta.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] A. Kunugi, K. Minami, M. Yasuzawa, K. Abe, T. Hirai: "Electrolytic reduction of beta, beta-bis(methylsulfonyl)styrene at mercuryelectrode in acetonitrile" Chem. Express. Vol. 4, No . 3. 189-192 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] A. Kunugi, M. Yasuzawa: "Electroreductive carboxylation of 1-methylthio-1-p-tolylsulfonyl-2-arylethenes in N, N-dimethylformamide" Denki Kagaku. Vol. 58, No. 3. 264-265 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] A. Kunugi, T. Myousei, M. Yasuzawa, K. Abe: "Electroreductive desulfurization and Carboxylation o alpha, beta-bis (methylsulfonyl) styrene in nonaqueous media" Denki Kagaku.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] A. Kunugi, M. Yasuzawa, Hiroshi Matsui: "Electrochemical carboxylation of beta-methylsulphenyl-beta-methylsulphinyl-styrene in N, N-dimethylformamide containing carbon dioxide" Electrochim. Acta.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] 椚章: "β、β-ビス(メチルスルホニル)スチレンのアセトニトリル/水銀電極系における電解還元反応" Chemistry Express. 4. 189-192 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Akira Kunugi: "Electroreductive Carboxylation of 1-Methylthio-1-p-tolylsulfonyl-2-arylethenes in N,N-Dimethylformamaide" Denki Kagaku. 58. 264-265 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] Mikito Yasuzawa: "Electrochemical Carboxylation of Some Sulfur-containing Olefines" Extended Abstracts of 40th ISE Meeting. 860-861 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Akira Kunugi: "Cathodic Desulfonylation of α.β-Bis(methylsulfonyl)styrene at Mercury Electrode in Nonaqueous Solvents" Review of Polarography. 35. 42-42 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] 椚章: Chemistry Express. 4. (1989)

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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