Trans-esterification reaction catalyzed by alkoxo(triphenylphosphine)copper(I) complexes.
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概要
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Alkoxocopper and phenoxocopper complexes ROCu (PPh<SUB>3</SUB>)<I><SUB>n</SUB></I> (PPh<SUB>3</SUB>=triphenylphosphine; <I>n</I>=1 for R=<I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB> or <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>; <I>n</I>=2 for R=CH<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>, CH<SUB>2</SUB>=CHCH<SUB>2</SUB>, C<SUB>6</SUB>H<SUB>5</SUB>CH<SUB>2</SUB>, or C<SUB>6</SUB>H<SUB>5</SUB>) react with esters undergoing exchange of the RO group with carboxylic esters. The alkoxocopper and phenoxocopper complexes are found to be excellent catalysts for the trans-esterification of carboxylic esters, dimethyl carbonate, and trimethyl phosphite with alcohols and phenols. A comparison of the ability of the isopropoxocopper complex as trans-esterification catalyst with that of aluminum isopropoxide and titanium isopropoxide shows the superiority of the isopropoxocopper complex. The rate of trans-esterification between <I>p</I>-nitrophenyl acetate and phenol follows the second-order rate law <I>R</I>=<I>k</I>[<I>p</I>-nitrophenyl acetate][phenol], the activation energy of the reaction being estimated to be 12.4 kcal/mol. A mechanism comprising a nucleophilic attack on the copper-bound carbonyl group of the ester by alcohol is proposed.
- 公益社団法人 日本化学会の論文
著者
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Yamamoto Takakazu
Research Laboratory Of Resouces Utilization Tokyo Institute Of Technology
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Yamamoto Akio
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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Kubota Minoru
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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