Deuterium Isotope Effects on the Redex Decomposition of Hydroxymercurated Propene and 2-Butenes in an Aqueous Solution
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概要
- 論文の詳細を見る
Kinetic deuterium isotope effects on the redox decomposition of hydroxymercurated propene, <I>cis</I>-, and <I>trans</I>-2-butenes in an aqueous solution (CH<SUB>3</SUB>CH(OH)CHRHg<SUP>+</SUP>→CH<SUB>3</SUB>COCH<SUB>2</SUB>R+Hg(0)+H<SUP>+</SUP>; R=H, CH<SUB>3</SUB>) were determined by following the reaction in situ by means of PMR spectroscopy. Taking advantage of the PMR characteristics, the identity of the reaction conditions was confirmed by comparing the rates for the reactant mixtures (<I>e.g.,</I> CH<SUB>3</SUB>CH(OH)CH<SUB>2</SUB>Hg<SUP>+</SUP>+CH<SUB>3</SUB>CD(OH)CH<SUB>2</SUB>Hg<SUP>+</SUP>). The mercurials, deuterated on either β-carbon (CH<SUB>3</SUB>CD(OH)CH<SUB>2</SUB>Hg<SUP>+</SUP>, CH<SUB>3</SUB>CD(OH)CHCH<SUB>3</SUB>Hg<SUP>+</SUP>) or α-carbon (CH<SUB>3</SUB>CH(OH)CDHHg<SUP>+</SUP>, CH<SUB>3</SUB>CH(OH)CDCH<SUB>3</SUB>Hg<SUP>+</SUP>), gave primary and secondary deuterium isotope effects of 1.35–1.40 and 1.17–1.19 respectively. A possible structure of the activated complex was proposed in accord with the observed nature of the intramolecular hydrogen shift.
- 公益社団法人 日本化学会の論文
著者
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Shinoda Sumio
Department Of Environmental Hygiene Faculty Of Pharmaceutical Sciences Okayama University
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Saito Yasukazu
Department Of Industrial Chemistry Faculty Of Engineering The University Of Tokyo
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Saito Yasukazu
Department of Synthetic Chemistry, Faculty of Engineering, University of Tokyo
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