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Volumn 350, Issue 17, 2008, Pages 2740-2746

Activation of elemental sulfur by electrogenerated cyanomethyl anion: Synthesis of substituted 2-aminothiophenes by the Gewald reaction

Author keywords

2 aminothiophenes; Electrogenerated cyanomethyl anion; Elemental sulfur; Gewald reaction; Ylidenemalononitriles

Indexed keywords


EID: 56749091753     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200800503     Document Type: Article
Times cited : (46)

References (65)
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    • D. Singh, S. Mohan, P. C. Sharma, J. Saravanan, Acta Pharm. Sci. 2007, 49, 29-38.
    • b) D. Singh, S. Mohan, P. C. Sharma, J. Saravanan, Acta Pharm. Sci. 2007, 49, 29-38.
  • 17
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    • K. Gewald, Z. Chem. 1962, 2, 305-306.
    • (1962) Z. Chem , vol.2 , pp. 305-306
    • Gewald, K.1
  • 35
    • 56749136589 scopus 로고
    • Universitè de Rennes
    • Q. T. Do, Thesis, Universitè de Rennes, 1988.
    • (1988) Thesis
    • Do, Q.T.1
  • 48
    • 56749118309 scopus 로고    scopus 로고
    • [24h]); theoretically, both anions can act as catalysts in this activation of sulfur, but we have not evidenced the presence of aminocrotononitrile in the cathodic solution after the work-up. As this reaction is very fast (<10 min of electrolysis, then addition of sulfur to the cathodic solution), it is probable that cyanomethyl anion has not enough time to dimerize.
    • [24h]); theoretically, both anions can act as catalysts in this activation of sulfur, but we have not evidenced the presence of aminocrotononitrile in the cathodic solution after the work-up. As this reaction is very fast (<10 min of electrolysis, then addition of sulfur to the cathodic solution), it is probable that cyanomethyl anion has not enough time to dimerize.
  • 52
    • 0000536423 scopus 로고    scopus 로고
    • 2-), while the following peaks seem to be related to the reduction of decomposition products: a) M. V. Merritt, D. T. Sawyer, Inorg. Chem. 1970, 9, 211-215;
    • 2-), while the following peaks seem to be related to the reduction of decomposition products: a) M. V. Merritt, D. T. Sawyer, Inorg. Chem. 1970, 9, 211-215;
  • 57
    • 56749172998 scopus 로고    scopus 로고
    • 8 shows two reduction peaks, the first at a potential of -0.75 V and the second at a potential of -1.15 V. After the addition of cyanomethyl anion, the two peaks desappeared.
    • 8 shows two reduction peaks, the first at a potential of -0.75 V and the second at a potential of -1.15 V. After the addition of cyanomethyl anion, the two peaks desappeared.
  • 58
    • 56749107971 scopus 로고    scopus 로고
    • In the cases in which the reduction potential of the ylidenemalononitrile is more negative of the first reduction potential of S8, it is possible to obtain the Gewald product by potentiostatic reduction of a solution of solvent-supporting electrolyte containing S8 and the ylidenemalononitrile. We have carried out the selective electrochemical reduction of S8 in the presence of 1b, in a MeCN/Et 4NPF6 0.1 mol dm-3 solution, at room temperature, under an N2 atmosphere, on a Pt cathode, at a potential of -0.8 V vs. SCE. After 0.4 F/mol of 1b, the electrolysis was stopped and, after 1 hour at room temperature, the usual work-up gave 2b in a quantitative yield. This methodology, that is, the direct cathodic reduction of elemental sulfur, is slightly more complicated with respect to the one described in this paper, as a reference electrode and the supporting electrolyte are necessary
    • 2 atmosphere, on a Pt cathode, at a potential of -0.8 V vs. SCE. After 0.4 F/mol of 1b, the electrolysis was stopped and, after 1 hour at room temperature, the usual work-up gave 2b in a quantitative yield. This methodology, that is, the direct cathodic reduction of elemental sulfur, is slightly more complicated with respect to the one described in this paper, as a reference electrode and the supporting electrolyte are necessary.
  • 62
    • 0002392276 scopus 로고
    • About the I-strain, see: a
    • About the I-strain, see: a) H. C. Brown, M. Gerstein, J. Am. Chem. Soc. 1950, 72, 2926-2933;
    • (1950) J. Am. Chem. Soc , vol.72 , pp. 2926-2933
    • Brown, H.C.1    Gerstein, M.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.