Bulletin of the Korean Chemical Society

  • 제12권1호
  • /
  • Pages.93-97
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  • 1991
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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The Effect of the Changing of C-O-C to C-S-C and C=O to C=S on Reactivity of 4-Nitrophenyl Benzoate with Alkali Metal Ethoxides in Ethanol

  • 발행 : 1991.02.20
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초록

Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides with 4-nitrophenyl benzoate, S-4-nitrophenyl thiobenzoate and 4-nitrophenyl thionbenzoate in ethanol at 25$^{\circ}$C. Substitution of S for O in the leaving group has not affected reactivity significantly, while the effect of the similar replacement in the acyl group has led to rate decrease by a factor of 10, although pronounced rate enhancements have been expected for both systems. The replacement of O by a polarizable S has also influenced the reactivity of the esters toward alkali metal ethoxides, i.e. the reactivity decreases as the size of the metal ion decreases. The alkali metal ions have showed inhibition effect instead of catalytic effect which would have been expected for the present system. The effect of replaced sulfur atom on the reactivity for the present system is attributed to the nature of hard and soft acids and bases.

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참고문헌

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피인용 문헌

  1. Kinetics and mechanism of the aminolysis of phenyl dithioacetate in aqueous solution vol.1991, pp.12, 1991, https://doi.org/10.1039/p29910001919
  2. Kinetics and Mechanism of the Base-Catalysed Cyclisation of 2-(Substituted benzoylamino)benzamides Giving Quinazolin-4-one and Quinazolin-4-thione Derivatives vol.2002, pp.11, 1991, https://doi.org/10.1002/1099-0690(200206)2002:11<1855::aid-ejoc1855>3.0.co;2-a
  3. Applications of Third Order Models in Solvolytic Reaction of Aliphatic Substituted Acyl Derivatives in 2,2,2-Trifluoroethanol-Ethanol Systems vol.24, pp.9, 2003, https://doi.org/10.5012/bkcs.2003.24.9.1293
  4. Alkali Metal Ion Catalysis in Nucleophilic Substitution Reactions of 5-Nitro-8-quinolyl Benzoate with Alkali Metal Ethoxides in Anhydrous Ethanol: Unusually High Na+ Ion Selectivity vol.29, pp.1, 1991, https://doi.org/10.5012/bkcs.2008.29.1.117