Relative Reactivities in the Addition of Free Trichloromethyl Radicals to Substituted Styrenes. An Attempt to Separate Polar and Resonance Effects

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概要

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• Relative reactivities in dibenzoyl peroxide-catalyzed addition of bromotrichloromethane to nine nuclearsubstituted styrenes have been investigated with unsubstituted styrene. The effect of <I>meta</I> substituents upon the relative rates was correlated with the simple Hammett equation using either σ or σ<SUP>+</SUP> constants. The relative rates of <I>para</I>-substituted styrenes, however, did not obey the simple Hammett relation, with the results best explained on the basis of polar (ρσ<SUP>+</SUP>) and resonance (<I>E</I><SUB>D</SUB>) terms. All <I>para</I> substituents examined increase the reactivity.<BR>log(<I>k</I>⁄<I>k</I><SUB>H</SUB>)=ρσ<SUP>+</SUP>+<I>E</I><SUB>D</SUB><BR>The <I>E</I><SUB>D</SUB> term shows a striking correlation with log<I>Q</I>, of the corresponding <I>para</I> styrene in Alfrey-Price′s <I>Q</I>-<I>e</I> scheme of free-radical copolymerization. That the polar term originates in charge-transfer interactions between the olefin and the electrophilic trichloromethyl radical and can be expressed by ρσ<SUP>+</SUP> is further supported by the evidence that charge-transfer energies of substituted styrenes showed good correlation with σ<SUP>+</SUP>. Factors influencing the reactivity have been discussed.

• 公益社団法人 日本化学会の論文

著者

• SAKURAI Hideki

  Department of Chemistry, Faculty of Science, Tohoku University

• Hosomi Akira

  Department Of Chemistry And Graduate School Of Chemistry University Of Tsukuba

• Sakurai Hideki

  Department Of Chemistiy Faculty Of Science Tohoku University

• Hayashi Shun-ichi

  Department of Chemistry, Faculty of Science, Tohoku University

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