Equilibrium and rate data on some arsenite transesterification reactions.
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概要
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The arsenite transesterification reaction As(OCH<SUB>3</SUB>)<SUB>3</SUB>+ HOR\rightleftharpoonsAs(OCH<SUB>3</SUB>)<SUB>2</SUB>OR+HOCH<SUB>3</SUB>(with R equaling benzyl and <I>t</I>-butyl) has been studied in acetonitrile solvent. With benzyl alcohol, <I>K</I>, Δ<I>H</I>°, and Δ<I>S</I>° are 3.6 (25°C), 5.0 kJ mol<SUP>−1</SUP> and 27 J mol<SUP>−1</SUP> K<SUP>−1</SUP> respectively; with <I>t</I>-butyl alcohol, the values are 0.36 (25°C), 4.0 kJ mol<SUP>−1</SUP>, and 5 J mol<SUP>−1</SUP> K<SUP>−1</SUP> respectively. The rate law for the approach to equilibrium in the case of benzyl alcohol is:<BR>\frac−<I>d</I>[As(OCH<SUB>3</SUB>)<SUB>3</SUB>]<I>dt</I>=<I>k</I><SUB>f</SUB>′[As(OCH<SUB>3</SUB>)<SUB>3</SUB>][HOCH<SUB>2</SUB>Ph]<SUP>2</SUP>−<I>k</I><SUB>r</SUB>′[As(OCH<SUB>3</SUB>)<SUB>2</SUB>(OCH<SUB>2</SUB>Ph)][HOCH<SUB>3</SUB>][HOCH<SUB>2</SUB>Ph].<BR>A mechanism which explains the unusual law has been postulated. The slower <I>t</I>-butyl alcohol reaction proceeds by a different mechanism which apparently involves catalysis by small amounts of water in the solvent. The steric effects are very significant.
- 公益社団法人 日本化学会の論文
著者
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Okumura Akiko
Department Of Chemistry Nara Women's University
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Edwards John
Department Of Biology University Of Washington
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Edwards John
Department of Chemistry, Brown University
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Rieger Philip
Department of Chemistry, Brown University
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Taylor Catherine
Department of Chemistry, Brown University
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Toyomi Yuiko
Department of Chemistry, Brown University
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