Presence or absence of a novel charge-transfer complex in the base-catalyzed hydrolysis of N-ethylbenzamide or ethyl benzoate

• Shinichi Yamabe,
• Wei Guan and
• Shigeyoshi Sakaki

Beilstein J. Org. Chem. 2013, 9, 185–196, doi:10.3762/bjoc.9.22

• )–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−(H2O)16 was employed. For X = O, three elementary processes and for X = NH four ones were obtained. The

• minimal model of TS1 was proposed and was found to be insensitive to n. Keywords: basic hydrolyses; DFT calculations; ethyl benzoate; N-ethylbenzamide; reactive intermediates; transition states; Introduction Basic hydrolyses of esters and amides have been extensively studied experimentally [1]. Use of

• calculations were carried out to shed light on the five points above, 1–5. As isoelectronic substrates, ethyl benzoate and N-ethylbenzamide were employed, of which the reactions are shown in Scheme 3. The former (ester) reaction has been studied well and its activation energy was reported to be 14.6 kcal/mol