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Volumn , Issue 4, 2003, Pages 627-633

New insight into the mechanism of the conjugate addition of benzenethiol to cyclic and acyclic enones and of the corresponding uranyl-salophen-catalysed version

Author keywords

Enones; Homogeneous catalysis; Kinetics; Michael addition; Uranium

Indexed keywords

ACETAMINOSALOL; AMINE; BASE; CHLOROFORM; CYCLOPENTENONE; ENONE; ION; KETONE; METAL; METAL COMPLEX; QUINUCLIDINE DERIVATIVE; THIOL; THIOPHENOL; TRIETHYLAMINE; UNCLASSIFIED DRUG; URANIUM;

EID: 0037325016     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/ejoc.200390102     Document Type: Article
Times cited : (30)

References (35)
  • 11
    • 85050272509 scopus 로고
    • (Eds. Eliel E. L. Wilen S. H. N. L. Allinger), Wiley, New York
    • H. Wynberg, in Topics in Stereochemistry, vol. 16 (Eds.: E. L. Eliel, S. H. Wilen, N. L. Allinger), Wiley, New York, 1986, pp. 87-129.
    • (1986) Topics in Stereochemistry , vol.16 , pp. 87-129
    • Wynberg, H.1
  • 28
    • 0013437084 scopus 로고    scopus 로고
    • note
    • In a number of kinetic runs (not reported in Table 1) carried out at benzenethiol concentrations on the order of 0.5 M, the third-order specific rates turned out to be higher by some 15-20% than those measured at lower concentrations. This finding might indicate the existence of a modest second-order contribution in benzenethiol, or might well be ascribed to non-ideal behaviour in the relatively concentrated benzenethiol solutions
  • 29
    • 0001694931 scopus 로고
    • 2Cl at 123 K (see: G. S. Denisov, N. S. Golnber, J. Mol. Struct. 1981, 75, 311-326). Under the given conditions the ion pair is in equilibrium with the hydrogen-bonded adduct.
    • (1981) J. Mol. Struct. , vol.75 , pp. 311-326
    • Denisov, G.S.1    Golnber, N.S.2
  • 31
    • 0002118048 scopus 로고    scopus 로고
    • Keto-enol equilibrium constants
    • (Ed.: Z. Rappoport), Wiley, New York1990
    • -7.9 have been reported for the keto/enol equilibrium involving cyclopentanone; see: J. Toullec, "Keto-Enol Equilibrium Constants" in The Chemistry of Enols (Ed.: Z. Rappoport), Wiley, New York, 1990, p. 321.
    • The Chemistry of Enols , pp. 321
    • Toullec, J.1
  • 33
    • 0013451606 scopus 로고    scopus 로고
    • note
    • Analogous results were observed with methyl vinyl ketone, which gave the addition product 4-(phenylthio)-2-butanone in virtually quantitative yield at a comparable rate. In the presence of the uranyl-salophen catalyst, however, the kinetics showed considerable scatter that was reduced, but not eliminated, when methyl vinyl ketone was freshly purified by distillation from calcium hydride in vacuo. Better reproducibility of results occurred also when ethyl vinyl ketone was distilled


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