Bulletin of the Korean Chemical Society

  • 제33권3호
  • /
  • Pages.843-847
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  • 2012
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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 Anilinolysis of Dibutyl Chlorothiophosphate in Acetonitrile

  • 투고 : 2011.12.13
  • 심사 : 2011.12.29
  • 발행 : 2012.03.20
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초록

The nucleophilic substitution reactions of dibutyl chlorothiophosphate (4S) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs;$k_H/k_D$) are primary normal ($k_H/k_D$ = 1.10-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of the chlorothiophosphates are discussed. The anilinolyses of P=S systems are compared with those of their P=O counterparts on the basis of the reactivities, thio effects, selectivity parameters, and DKIEs.

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피인용 문헌

  1. Kinetics and Mechanism of Pyridinolyses of Ethyl Methyl and Ethyl Propyl Chlorothiophosphates in Acetonitrile vol.34, pp.11, 2013, https://doi.org/10.5012/bkcs.2013.34.11.3372
  2. Kinetics and Mechanism of the Anilinolyses of O-Methyl, O-Propyl and O-Isopropyl Phenyl Phosphonochloridothioates in Acetonitrile vol.34, pp.4, 2013, https://doi.org/10.5012/bkcs.2013.34.4.1096
  3. Pyridinolyses of O-Propyl and O-Isopropyl Phenyl Phosphonochloridothioates in Acetonitrile vol.34, pp.9, 2013, https://doi.org/10.5012/bkcs.2013.34.9.2811
  4. -butyl phenyl phosphonochloridothioate in acetonitrile: Synthesis, characterization, kinetic study, and reaction mechanism vol.30, pp.10, 2017, https://doi.org/10.1002/poc.3679
  5. Kinetics and Mechanism of the Anilinolysis of Dipropyl Chlorophosphate in Acetonitrile vol.33, pp.6, 2012, https://doi.org/10.5012/bkcs.2012.33.6.1879
  6. Kinetics and Mechanism of the Pyridinolysis of Diisopropyl Chlorothiophosphate in Acetonitrile vol.33, pp.10, 2012, https://doi.org/10.5012/bkcs.2012.33.10.3203
  7. Kinetics and Mechanism of Anilinolyses of Ethyl Methyl, Ethyl Propyl and Diisopropyl Chlorothiophosphates in Acetonitrile vol.34, pp.12, 2012, https://doi.org/10.5012/bkcs.2013.34.12.3811
  8. Kinetics and Mechanism of Anilinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile vol.35, pp.9, 2012, https://doi.org/10.5012/bkcs.2014.35.9.2797