Bulletin of the Korean Chemical Society

  • 제33권10호
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  • Pages.3203-3207
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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 Pyridinolysis of Diisopropyl Chlorothiophosphate in Acetonitrile

  • 투고 : 2012.04.25
  • 심사 : 2012.07.02
  • 발행 : 2012.10.20
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초록

The nucleophilic substitution reactions of diisopropyl chlorothiophosphate (5) with X-pyridines have been kinetically studied in MeCN at $35.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for the substituent X variations in the nucleophiles show biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 5 exhibits great negative deviation from the Taft plot. A concerted $S_N2$ mechanism is proposed involving a change of the attacking direction of the X-pyridines from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines.

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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. 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
  3. Kinetics and Mechanism of Pyridinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile vol.35, pp.2, 2014, https://doi.org/10.5012/bkcs.2014.35.2.483