Bulletin of the Korean Chemical Society

  • 제12권2호
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  • Pages.182-188
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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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MO Theoretical Studies on the Benzylic and Resonance Shunt Effects

  • 발행 : 1991.04.20
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초록

The reactions of aniline with benzyl and phenacyl compounds are studied by the AM1 method. Two types of modeling were adopted: Cation-neutral, in which a proton is attached to the leaving group F and anion-neutral model, in which aniline was replaced by phenoxide with Cl as the leaving group. The cation-neutral model represented the reactvery well, reproducing the various solution-phase experimental results. In the benzyl system, the ${\pi}$-electrons of the two rings (X-ring in the nucleophile and Y-ring in the substrate) interact conjugatively in the transition state (TS) resulting in a bond contraction of the $C_{\alpha}-C_{Y1}$ bond (benzylic effect), whereas in the phenacyl system the ${\pi}$ electrons of the X-ring delocalizes more efficiently into the carbonyl group than into the Y-ring (resonance shunt effect) with a bond contraction of the $C_{\alpha}-C_{\beta}$ bond. The bond contraction in the benzylic effect was substantially greater than that in the resonance shunt effect. The TS was rather loose for benzyl while it was tighter for phenacyl system. Various bond length changes with substituents in the TS were, however, found to be irregular.

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피인용 문헌

  1. Theoretical studies of the effects ofortho-methyl substitution onSN1 andSN2 processes at primary and secondary benzylic carbons vol.6, pp.9, 1993, https://doi.org/10.1002/poc.610060904
  2. Theoretical studies of the identity allyl transfer reactions vol.8, pp.7, 1995, https://doi.org/10.1002/poc.610080706