Bulletin of the Korean Chemical Society

  • 제32권5호
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  • Pages.1539-1542
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  • 2011
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Kinetics and Mechanism of the Aminolysis of O-Methyl S-Aryl Thiocarbonates in Acetonitrile

  • Oh, Hyuck-Keun (Department of Chemistry, Research Institute of Physics and Chemistry, Chonbuk National University)
  • 투고 : 2011.02.26
  • 심사 : 2011.03.16
  • 발행 : 2011.05.20
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초록

The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0$^{\circ}C$. The ${\beta}_X$(${\beta}_{nuc}$) values are in the range 0.62-0.80 with a negative cross-interaction constant, ${\rho}_{XZ}$ = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles ($XC_6H_4CH_2ND_2$) are large, $k_H/k_D$ = 1.29-1.75, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the MeO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.

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  6. Kinetics and Reaction Mechanism for Aminolysis of Benzyl 4-Pyridyl Carbonate in H2O: Effect of Modification of Nucleofuge from 2-Pyridyloxide to 4-Pyridyloxide on Reactivity and Reaction Me vol.33, pp.7, 2011, https://doi.org/10.5012/bkcs.2012.33.7.2269
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  8. A Kinetic Study on Aminolysis of t-Butyl 4-Pyridyl Carbonate and Related Compounds: Effect of Leaving and Nonleaving Groups on Reaction Mechanism vol.33, pp.9, 2011, https://doi.org/10.5012/bkcs.2012.33.9.2971
  9. Kinetic Study on Nucleophilic Substitution Reactions of 4-Nitrophenyl X-Substituted-2-Methylbenzoates with Cyclic Secondary Amines in Acetonitrile: Reaction Mechanism and Failure of Reactivity-Selecti vol.35, pp.1, 2014, https://doi.org/10.5012/bkcs.2014.35.1.93
  10. Reactions of 4‐NITROPHENYL 5‐substituted Furan‐2‐carboxylates with R 2 NH / R 2 NH 2+ in 20 mol% DMSOhttps://doi.org/10.1002/bkcs.12296