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Pregled bibliografske jedinice broj: 690486

Chlorination of N-Methylacetamide and Amide-Containing Pharmaceuticals : Quantum-Chemical Study of the Reaction Mechanism


Šakić, Davor; Šonjić, Pavica; Tandarić, Tana; Vrček, Valerije
Chlorination of N-Methylacetamide and Amide-Containing Pharmaceuticals : Quantum-Chemical Study of the Reaction Mechanism // The journal of physical chemistry. A, 118 (2014), 12; 2367-2376 doi:10.1021/jp5012846 (međunarodna recenzija, članak, znanstveni)


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Naslov
Chlorination of N-Methylacetamide and Amide-Containing Pharmaceuticals : Quantum-Chemical Study of the Reaction Mechanism

Autori
Šakić, Davor ; Šonjić, Pavica ; Tandarić, Tana ; Vrček, Valerije

Izvornik
The journal of physical chemistry. A (1520-6106) 118 (2014), 12; 2367-2376

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
hypochlorous acid ; tautomerization ; iminol form ; N-chloroamides ; computational chemistry

Sažetak
Chlorination of amides is of utmost importance in biochemistry and environmental chemistry. Despite the huge body of data, the mechanism of reaction between amides and hypochlorous acid in aqueous environment remains unclear. In this work, the three different reaction pathways for chlorination of N-methylacetamide by HOCl have been considered: the one-step N-chlorination of amide, the chlorination via O-chlorinated intermediate, and the N-chlorination of iminol intermediate. The high-level quantum chemical G3B3 composite procedure, double hybrid B2- PLYPD, B2K-PLYP methods, and global hybrid M06-2X and BMK methods have been employed. The calculated energy barriers have been compared to the experimental value of deltaG#298 ≈ 87 kJ/mol which corresponds to reaction rate constant kr ≈ 0.0036 M-1s-1. Only the mechanism in which the iminol form of N-methylacetamide reacts with HOCl is consistent (deltaG#298 = 87.3 kJ/mol at G3B3 level) with experimental results. The analogous reaction mechanism has been calculated as the most favorable pathway in the chlorination of small-sized amides and amide-containing pharmaceuticals: carbamazepine, acetaminophen, and phenytoin. We conclude that the formation of iminol intermediate followed by its reaction with HOCl is the general mechanism of N-chlorination for a vast array of amides.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Ustanove
Farmaceutsko-biokemijski fakultet, Zagreb

Profili:

Avatar Url Valerije Vrček (autor)

Avatar Url Davor Šakić (autor)

Avatar Url Tana Tandarić (autor)

Citiraj ovu publikaciju

Šakić, Davor; Šonjić, Pavica; Tandarić, Tana; Vrček, Valerije
Chlorination of N-Methylacetamide and Amide-Containing Pharmaceuticals : Quantum-Chemical Study of the Reaction Mechanism // The journal of physical chemistry. A, 118 (2014), 12; 2367-2376 doi:10.1021/jp5012846 (međunarodna recenzija, članak, znanstveni)
Šakić, D., Šonjić, P., Tandarić, T. & Vrček, V. (2014) Chlorination of N-Methylacetamide and Amide-Containing Pharmaceuticals : Quantum-Chemical Study of the Reaction Mechanism. The journal of physical chemistry. A, 118 (12), 2367-2376 doi:10.1021/jp5012846.
@article{article, year = {2014}, pages = {2367-2376}, DOI = {10.1021/jp5012846}, keywords = {hypochlorous acid, tautomerization, iminol form, N-chloroamides, computational chemistry}, journal = {The journal of physical chemistry. A}, doi = {10.1021/jp5012846}, volume = {118}, number = {12}, issn = {1520-6106}, title = {Chlorination of N-Methylacetamide and Amide-Containing Pharmaceuticals : Quantum-Chemical Study of the Reaction Mechanism}, keyword = {hypochlorous acid, tautomerization, iminol form, N-chloroamides, computational chemistry} }

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus
  • MEDLINE


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