Naslov
The chlorination of amides by HOCl

Autori
Vrček, Valerije

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, neobjavljeni rad, stručni

Skup
Summer school 2012 AvH-Linkage Program on "Computational Life Sciences on Open Shell Intermediates"

Mjesto i datum
Primošten, Hrvatska, 29.08.2013. - 01.09.2013

Vrsta sudjelovanja
Pozvano predavanje

Vrsta recenzije
Nije recenziran

Ključne riječi
reaction mechanism; computational chemistry; N-chlorination; amides

Sažetak
The N-chlorination of amines follows the mechanism via the cyclic transition state structure in which water molecules assist the simultaneous transfer of hydrogen atoms coupled with the N-Cl bond formation. Both experimental and theoretical studies have postulated the presence of water in the transition state for the aqueous chlorination of amines by HOCl. In order to reproduce the experimental results, the inclusion of two water molecules is mandatory in the solvent model calculations. However, the analogous mechanism is not operative for N-chlorination of amides. In the case of N-methyl-acetamide (NMA), the calculated energy barrier for the process which involves the transition state structure with the cyclic arrangement is 232.8 kJ/mol. This calculated value is in a strong disagreement to the experimental barrier of ca. 89 kJ/mol. Therefore, we have searched for the mechanism of N-chloramide formation which would fit to the available experimental data.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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