European Journal of Chemistry 2012, 3(3), 348-355. doi:10.5155/eurjchem.3.3.348-355.638

Theoretical density functional study of gas-phase tautomerization and acidity of 5-methylhydantoin and its thio derivatives


Zaki Sulieman Safi (1,*)

(1) Department of Chemistry, Faculty of Science, Al Azhar University-Gaza, 1277, Gaza, Palestine
(*) Corresponding Author

Received: 22 May 2012, Accepted: 21 Jul 2012, Published: 30 Sep 2012

Abstract


Tautomerization and acidities of various 5-methylhydantoins and their thio derivatives were predicted using Density Functional Theory (DFT). The functional used was B3LYP and the basis set for all atoms was 6-311+(d,p). Single point energy computations were performed at the 6-311+G(2df,2p) basis set. The relative stabilities of the different tautomers of the 2,4-dioxo, 2-thio-4-oxo, 4-thio-2-oxo and 2,4-dithio derivatives of the deprotonated 5-methylhydantoin have been studied. In all cases, the most stable deprotonated conformers are the oxo-thione, the dioxo or the dithio. As for the neutral and the protonated 5-methylhydantoin-thio derivatives, the tautomerization activation barriers are high enough as to conclude that the oxo-thione structures should be found in the gas phase. It was revealed that the ring-nitrogen atom at position 3 (N3) is more acidic than that at position 1 (N1), hence 5-methylhydantoin thio derivatives in the gas phase are an N3-acid. It has been found that the 2,4-dithio species is the most acidic compound among all the investigated compounds. The acidity values were found to be 343 (2O4O), 337 (2S4O), 336 (2O4S) and 332 kcal/mol (2S4S).

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Keywords


DFT; B3LYP; Acidity; Deprotonation; Tautomerization; 5-Methylhydantoin

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DOI: 10.5155/eurjchem.3.3.348-355.638

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Citations

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[1]. Anife Ahmedova, Petja Marinova, Marin Marinov, Neyko Stoyanov
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[2]. Zaki S. Safi, Subhia J. Al Hasanat, Nuha A. Wazzan
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[3]. Zaki S. Safi, Salama Omar, Subhia J. Al Hasanat, Nuha Wazzan, Abdesslem Jedidi
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How to cite


Safi, Z. Eur. J. Chem. 2012, 3(3), 348-355. doi:10.5155/eurjchem.3.3.348-355.638
Safi, Z. Theoretical density functional study of gas-phase tautomerization and acidity of 5-methylhydantoin and its thio derivatives. Eur. J. Chem. 2012, 3(3), 348-355. doi:10.5155/eurjchem.3.3.348-355.638
Safi, Z. (2012). Theoretical density functional study of gas-phase tautomerization and acidity of 5-methylhydantoin and its thio derivatives. European Journal of Chemistry, 3(3), 348-355. doi:10.5155/eurjchem.3.3.348-355.638
Safi, Zaki. "Theoretical density functional study of gas-phase tautomerization and acidity of 5-methylhydantoin and its thio derivatives." European Journal of Chemistry [Online], 3.3 (2012): 348-355. Web. 16 Nov. 2019
Safi, Zaki. "Theoretical density functional study of gas-phase tautomerization and acidity of 5-methylhydantoin and its thio derivatives" European Journal of Chemistry [Online], Volume 3 Number 3 (30 September 2012)

DOI Link: https://doi.org/10.5155/eurjchem.3.3.348-355.638

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