The Reaction of β-Hydroxyalkylmercuric Perchlorate with Sodium Formate in an Aqueous Solution
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概要
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The reaction of 2-hydroxy-1-propylmercuric perchlorate with sodium formate in an aqueous solution was found to be a redox-type reaction: CH<SUB>3</SUB>CH(OH)CH<SUB>2</SUB>HgClO<SUB>4</SUB>+HCOONa=CH3CH=CH2+Hg(0)+CO<SUB>2</SUB>+H<SUB>2</SUB>O+NaClO<SUB>4</SUB>. The concentration of the mercurial coordinated by the formate ion was determined <I>in situ</I> by analyzing the geminal <SUP>199</SUP>Hg-<SUP>1</SUP>H spin-coupling constant. By changing the ratio of [CH<SUB>3</SUB>CH(OH)CH<SUB>2</SUB>HgClO<SUB>4</SUB>]/[HCOONa], the initial reaction rate was confirmed to be first-order with respect to the formato-mercurial: <I>v</I>=<I>k</I>[CH<SUB>3</SUB>CH(OH)-CH<SUB>2</SUB>HgOCOH]. From the variation in <I>k</I> with the temperature, the values of <I>E<SUB>a</SUB></I>=17.5 kcal mol<SUP>−1</SUP> and <I>A</I>=4.0×10<SUP>8</SUP> s<SUP>−1</SUP> were obtained. On the grounds of the kinetic isotope effect for DCOONa and the stereochemical study with <I>threo</I>- and <I>erythro</I>-CH<SUB>3</SUB>CH(OH)CHCH<SUB>3</SUB>HgClO<SUB>4</SUB>, a mechanism is proposed in which the reaction proceeds solely through the unimolecular redox-decomposition of the formato-mercurial, involving an anti-elimination of olefin coupled with a two-electron transfer from the formate ligand to the mercurial.
- 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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