Presence or absence of a novel charge-transfer complex in the base-catalyzed hydrolysis of N-ethylbenzamide or ethyl benzoate.
抄録
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.
収録刊行物
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- Beilstein journal of organic chemistry
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Beilstein journal of organic chemistry 9 185-196, 2013-01
Beilstein-Institut
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詳細情報 詳細情報について
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- CRID
- 1050282810741141888
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- NII論文ID
- 120005242486
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- ISSN
- 18605397
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- HANDLE
- 2433/171151
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- 本文言語コード
- en
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- 資料種別
- journal article
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- データソース種別
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- IRDB
- CiNii Articles