Substituent effects. 22. The solvolysis of .ALPHA.-t-butylbenzyl tosylates.

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• The rates of solvolysis of α-<I>t</I>-butylbenzyl tosylates were determined in 80% aqueous acetone (80A) and 80% aqueous ethanol (80E) for an extended series of substituents. The substituent effect can be linearly correlated in terms of the Yukawa–Tsuno LArSR relationship, with a ρ value of −5.542 and an <I>r</I> value of 1.093 in 80A, and −5.650 and 1.106 in 80E, respectively. The large negative ρ and exalted <I>r</I> values suggest the operation of the <I>k</I><SUB>c</SUB> mechanism in this solvolysis without nucleophilic solvent assistance and methyl participation. From a comparison of the substituent effects, the exalted <I>r</I> value of 1.15 observed in the solvolysis of α-methylbenzyl chlorides can be attributed to the enhanced resonance demand characteristic of secondary benzylic system rather than to a correlational artifact arising from nonlinearity due to S<SUB>N</SUB>1–S<SUB>N</SUB>2 mechanistic change. The solvolysis of this system can be utilized as an appropriate reference system for the accurate estimation of σ<SUP>+</SUP> constants in various solvents.

• 公益社団法人 日本化学会の論文

著者

• FUJIO Mizue

  Department of Chemistry, Faculty of Science, Kyushu University

• Tsuno Yuho

  Department Of Chemistry Faculty Of General Education Kumamoto University

• Tsuji Yutaka

  Laboratory of Chemistry, College of General Education, Kyushu University

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