Substituent effects in the decomposition of t-alkyl t-butyl peroxides.

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概要

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• The decomposition rates and products of various <I>t</I>-alkyl <I>t</I>-butyl peroxides were examined in cumene at several temperatures. The decomposition of these peroxides took place homolytically, depending on the structure of the <I>t</I>-alkoxyl moieties (RC(CH<SUB>3</SUB>)<SUB>2</SUB>–O), and was retarded in the order: R=(CH<SUB>3</SUB>)<SUB>3</SUB>CCH<SUB>2</SUB>>(CH<SUB>3</SUB>)<SUB>2</SUB>CH>CH<SUB>3</SUB>CH<SUB>2</SUB>CH<SUB>2</SUB>>PhCH<SUB>2</SUB>>CH<SUB>3</SUB>CH<SUB>2</SUB>>ClCH<SUB>2</SUB>>CH<SUB>3</SUB>. The rate constants for the electron-donating alkyl substitutents at 150 °C are correlated very well to a Taft equation (log<I>k</I><SUB>d</SUB>=−10.93 Σσ<SUP>*</SUP>−6.61 (correlation coefficient of 0.9501)), which is fairly different from the equation log<I>k</I><SUB>d</SUB>=−10.131 Σσ<SUP>*</SUP>−3.422 for electorn-withdrawing polar substituents. From this correlation and a product analysis, the nature of the polar character at the transition state of the decomposition is discussed.

• 公益社団法人 日本化学会の論文

著者

• Higuchi Yoshiki

  Chemical & Explosives Research Laboratory, Nippon Oil & Fats Co., Ltd.

• Matsuyama Kazuo

  Chemical & Explosives Research Laboratory, Nippon Oil & Fats Co., Ltd.

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• Synthesis and thermal decomposition of di-t-butyl peroxydicarbonate.
• Substituent effects in the decomposition of t-alkyl t-butyl peroxides.

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