Substituent effects. XVIII. The resonance demand in the acetolysis of neophyl brosylates.

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概要

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• The substituent effect in the acetolysis of neophyl brosylates was analyzed statistically based on the Yukawa–Tsuno LArSR equation. Though the Brown ρ<SUP>+</SUP>σ<SUP>+</SUP> equation did not provide a linear correlation, the LArSR equation gave an excellent linear correlation with an <I>r</I> value of 0.57, substantiating our basic LArSR concept of varying resonance demands with different systems. For a statistical examination of the reliability of this nonunity <I>r</I> value, the change in the standard deviation of the LArSR correlation was followed as a function of varying <I>r</I> by an iterative least-squares method. The <I>r</I> value of the neophyl solvolysis must have sufficient statistical significance to distinguish between the LArSR and simple Brown ρ<SUP>+</SUP>σ<SUP>+</SUP> correlations of this system. The significance of the best-fit correlation was found to strongly depend upon the number and combination as well as the range of the effective substituents. The study was extended to various aryl-assisted processes of complex mechanisms, solvolyses of 2-arylethyl, 2-aryl-1-methylethyl, 2-aryl-1-methylpropyl, and (1-arylcyclobutyl)methyl arenesulfonates. A precise dissection analysis of non-crossover <I>k</I><SUB>Δ</SUB> and <I>k</I><SUB>s</SUB> processes has been realized by the Gauss–Newton type nonlinear least-squares method based on the assumption of LArSR correlations for both processes. The generality of the unique <I>r</I><SUB>Δ</SUB> value of neophyl solvolysis was verified regarding these β-aryl-assisted processes. The substituent effect on the <I>k</I><SUB>Δ</SUB> process can be characterized far more appropriately in terms of the \barσ<SUB>Δ</SUB> of <I>r</I>=0.6, rather than σ<SUP>+</SUP> of <I>r</I>=1.00.

• 公益社団法人 日本化学会の論文

著者

• Mishima Masaaki

  Department Of Chemistry And Physics Of Condensed Matter Graduate School Of Sciences Kyushu Universit

• FUJIO Mizue

  Department of Chemistry, Faculty of Science, Kyushu University

• Tsuno Yuho

  Department Of Chemistry Faculty Of General Education Kumamoto University

• Goto Mutsuo

  Department of Chemistry, Faculty of Science, Kyushu University

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