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dc.contributor.author | Yamabe, Shinichi | en |
dc.contributor.author | Guan, Wei | en |
dc.contributor.author | Sakaki, Shigeyoshi | en |
dc.contributor.alternative | 山邊, 信一 | ja |
dc.date.accessioned | 2013-03-05T07:31:25Z | - |
dc.date.available | 2013-03-05T07:31:25Z | - |
dc.date.issued | 2013-01 | - |
dc.identifier.issn | 1860-5397 | - |
dc.identifier.uri | http://hdl.handle.net/2433/171151 | - |
dc.description.abstract | Reaction paths of base-catalyzed hydrolyses of isoelectronic substrates, Ph-C(=O)-X-Et [X = O (ethyl benzoate) and X = NH (N-ethylbenzamide)], were traced by DFT calculations. To simulate bond interchanges accompanied by proton transfers, a cluster model of Ph-C(=O)-X-Et + OH(-)(H(2)O)(16) was employed. For X = O, three elementary processes and for X = NH four ones were obtained. The rate-determining step of X = O is the first TS (TS1, the OH(-) addition step), while that of X = NH is TS2. TS2 of X = NH leads to a novel Mulliken charge-transfer complex, Ph-(OH)(O=)C∙∙∙N(H(2))-Et. The superiority or inferiority between the direct nucleophilic process or the general base-catalyzed process for TS1 was examined with the model Ph-C(=O)-X-Et + OH(-)(H(2)O)(n), n = 3, 5, 8, 12, 16, 24 and 32. The latter process was calculated to be more favorable regardless of the number (n, except n = 3) of water molecules. The counter ion Na(+) works unfavorably on the ester hydrolysis, particularly on TS1. A minimal model of TS1 was proposed and was found to be insensitive to n. | en |
dc.format.mimetype | application/pdf | - |
dc.language.iso | eng | - |
dc.publisher | Beilstein-Institut | en |
dc.rights | © 2013 Yamabe et al; licensee Beilstein-Institut. | en |
dc.rights | This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. | en |
dc.rights | The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc) | en |
dc.subject | basic hydrolyses | en |
dc.subject | DFT calculations | en |
dc.subject | ethyl benzoate | en |
dc.subject | N-ethylbenzamide | en |
dc.subject | reactive intermediates | en |
dc.subject | transition states | en |
dc.title | Presence or absence of a novel charge-transfer complex in the base-catalyzed hydrolysis of N-ethylbenzamide or ethyl benzoate. | en |
dc.type | journal article | - |
dc.type.niitype | Journal Article | - |
dc.identifier.jtitle | Beilstein journal of organic chemistry | en |
dc.identifier.volume | 9 | - |
dc.identifier.spage | 185 | - |
dc.identifier.epage | 196 | - |
dc.relation.doi | 10.3762/bjoc.9.22 | - |
dc.textversion | publisher | - |
dc.identifier.pmid | 23400273 | - |
dcterms.accessRights | open access | - |
出現コレクション: | 学術雑誌掲載論文等 |
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