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邻醌与丙二酸亚异丙酯衍生物的电化学诱导迈克尔反应的动力学研究。高氧化态儿茶酚的合成。

Kinetic study of electrochemically induced michael reactions of o-quinones with Meldrum's acid derivatives. Synthesis of highly oxygenated catechols.

作者信息

Nematollahi D, Shayani-jam H

机构信息

Faculty of Chemistry, University of Bu-Ali-Sina, Hamadan, 65174,

出版信息

J Org Chem. 2008 May 2;73(9):3428-34. doi: 10.1021/jo800115n. Epub 2008 Apr 9.

Abstract

Electrochemical oxidation of catechols has been studied in the presence of Meldrum's acid derivatives as nucleophiles in aqueous solution, by means of cyclic voltammetry and controlled-potential coulometry. Catechols in the Michael addition reaction react with Meldrum's acids to form adducts that can undergo electrooxidation. Such products were obtained in good yields as confirmed by controlled potential electrosynthesis. Such products can be generated in aqueous solutions by means of electrosynthesis, using a carbon electrode in an undivided cell. Furthermore, the homogeneous rate constants of the chemical reaction interposed between electron transfers were estimated by comparing the experimental cyclic voltammetric curves with the digitally simulated ones.

摘要

在水溶液中,以丙二酸亚异丙酯衍生物作为亲核试剂,通过循环伏安法和控制电位库仑法研究了儿茶酚的电化学氧化。儿茶酚在迈克尔加成反应中与丙二酸亚异丙酯反应形成可进行电氧化的加合物。通过控制电位电合成证实,此类产物产率良好。使用未分隔电解池中的碳电极,通过电合成可在水溶液中生成此类产物。此外,通过将实验循环伏安曲线与数字模拟曲线进行比较,估算了电子转移之间化学反应的均相速率常数。

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