| The cis-trans Isomerisation of Homologous 2-Hydroxycycloalkanecarboxylic Acids under Basic Conditions |
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| 作者姓名： | GYARMATI Cs.Zsuzsanna PLINKIstván BOKROS Attila MARTINEK A.Tamás BERNTH Gábor Gábor |
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| 作者单位： | Institute of Pharmaceutical Chemistry University of Szeged，Szeged POB 121，H-6701 HungaryResearch Group for Heterocyclic Chemistry of the Hungarian Academy of Sciences and University of Szeged，Szeged POB 121，H-6701 Hungaryc，Department of Organic Chemistry，University of Szeged，Szeged，Dóm tér 8，H-6720 Hungary，Institute of Pharmaceutical Chemistry，University of Szeged，Szeged POB 121，H-6701 HungaryResearch Group for Heterocyclic Chemistry of the Hungarian Academy of Sciences and University of Szeged，Szeged POB 121，H-6701 Hungaryc，Institute of Pharmaceutical Chemistry，University of Szeged，Szeged POB 121，H-6701 Hungary，Institute of Pharmaceutical Chemistry，University of Szeged，Szeged POB 121，H-6701 HungaryResearch Group for Heterocyclic Chemistry of the Hungarian Academy of Sciences and University of Szeged，Szeged POB 121，H-6701 Hungaryc |
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| 基金项目： | Project supported by the National Science Fund of Hungary （Nos. T034422 and T034184）. |
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| 摘 要： | The cis→trans isomerisation of homologous 2-hydroxycycloalkanecarboxylic acids in strongly basic aqueous solution was studied starting from the cis isomers. It was found that the cyclopentane, cyclohexane and cycloheptane homologues afforded synthetically useful amounts of the trans acids and the procedure resulted in relatively small quantities of the corresponding olefinic acids. In contrast, the isomerisation of the cis-2-hydroxycyclooctanecarboxylic acid produced roughly equal amounts of the cis and trans isomers and the 1-cyclooctenecarboxylic acid at equilibrium. Molecular modelling with the PM3 semiempirical method of the reactants, products and the intermediates applying explicit water molecules as reaction medium gave a fair estimate for the rate sequence of the idealised （dehydration-free） isomerisation reactions in aqueous base solution.
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| 关 键 词： | 几何异构化 碱催化作用 反应机理 分子模型 2-羟基环链烷羧酸 |
| 收稿时间： | 2005-12-07 |
| 修稿时间： | 2005-12-072006-03-03 |
The cis-trans Isomerisation of Homologous 2-Hydroxycycloalkanecarboxylic Acids under Basic Conditions |
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| GYARMATI Cs.Zsuzsanna.The cis-trans Isomerisation of Homologous 2-Hydroxycycloalkanecarboxylic Acids under Basic Conditions[J].Chinese Journal of Chemistry,2006,24(12):1792-1795. |
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| Authors: | GYARMATI CsZsuzsanna |
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| Institution: | GYARMATI Cs.Zsuzsanna~ |
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| Abstract: | The cis→trans isomerisation of homologous 2‐hydroxycycloalkanecarboxylic acids in strongly basic aqueous solution was studied starting from the cis isomers. It was found that the cyclopentane, cyclohexane and cycloheptane homologues afforded synthetically useful amounts of the trans acids and the procedure resulted in relatively small quantities of the corresponding olefinic acids. In contrast, the isomerisation of the cis‐2‐hydroxycyclooctanecarboxylic acid produced roughly equal amounts of the cis and trans isomers and the 1‐cyclooctenecarboxylic acid at equilibrium. Molecular modelling with the PM3 semiempirical method of the reactants, products and the intermediates applying explicit water molecules as reaction medium gave a fair estimate for the rate sequence of the idealised (dehydration‐free) isomerisation reactions in aqueous base solution. |
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| Keywords: | geometric isomerisation base catalysis reaction mechanism molecular modelling |
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