Mechanism of formation of biocidal imidazolidin-4-one derivatives: An ab initio density-functional theory

Akdağ, Akın
Worley, S. D.
N-halamine chemistry has been a research topic of considerable importance in these laboratories for over 2 decades because N-halamine compounds are very useful in preparing biocidal materials. To understand the utility of these compounds, the stabilities and mechanism of halogenation of cyclic N-halamine compounds should be resolved. The important precursor biocidal compound, 2,2,5,5-tetramethylimidazolidin-4-one (TMIO) was considered as a model in this theoretical study. The thermodynamic and kinetic products of monohalogenation were investigated along with tautomerization of TMIO and succinimide theoretically at the level of B3LYP/6-311 + G(2d,p). Solvation effects (water and chloroform) were included using the CPCM solvation model with UAKS cavities. Several mechanisms have been proposed for the chlorine migration from the 3-position (kinetic product) to the 1-position (thermodynamic product) of the TMIO ring. The results are in agreement with experimental NMR data.


The stabilities of N-Cl bonds in biocidal materials
Akdağ, Akın; McKee, Michael L.; Worley, S. D. (American Chemical Society (ACS), 2006-05-01)
N-halamine chemistry has been a research topic of considerable importance in these laboratories for over two decades. N-halamine compounds are useful in preparing biocidal materials. There are three N-Cl moieties available in cyclic N-halamine compounds: imide, amide, and amine. The stabilities toward the release of free halogen have been experimentally shown to decrease in the order amine > amide > imide. In this work, this generalization has been tested theoretically at the level of B3LYP/6-31+G(d) and us...
Toward Designed Singlet Fission: Electronic States and Photophysics of 1,3-Diphenylisobenzofuran
Schwerin, Andrew F.; Johnson, Justin C.; Smith, Milicent B.; Sreearunothai, Paiboon; Popovic, Duska; Cerny, Jiri; Havlas, Zdenek; Paci, Irina; Akdağ, Akın; MacLeod, Matthew K.; Chen, Xudong; David, Donald E.; Ratner, Mark A.; Miller, John R.; Nozik, Arthur J.; Michl, Josef (American Chemical Society (ACS), 2010-01-01)
Single crystal molecular structure and solution photophysical properties are reported for 1,3-diphenylisobenzofuran (1), of interest its a model compound in studies of singlet fission. For the ground state of I and of its radical cation (1(+center dot)) and anion (1(-center dot)), we report the UV-visible absorption spectra, and for neutral 1, also the magnetic circular dichroism (MCD) and the decomposition of the absorption spectrum into purely polarized components, deduced from fluorescence polarization. ...
Synthesis of Functionalized Novel alpha-Amino-beta-alkoxyphosphonates through Regioselective Ring Opening of Aziridine-2-phosphonates
Polat-Cakir, Sidika; Beksultanova, Nurzhan; Doğan, Özdemir (Wiley, 2019-11-01)
Aziridines are highly useful compounds as building blocks for the synthesis of important organic compounds. Amino acid synthesis by aziridine ring opening reaction is a good example to the use of aziridines. Although this reaction is studied by many groups, the synthesis of amino phosphonic acids is less explored. In this study, we have carried out the ring opening reaction of aziridinyl phosphonates with a variety of alcohols including the more functional propargylic and allylic alcohols. These reactions p...
The barrier height, unimolecular rate constant, and lifetime for the dissociation of HN2
Bozkaya, Ugur; Turney, Justin M.; Yamaguchi, Yukio; Schaefer, Henry F. (AIP Publishing, 2010-02-14)
Although never spectroscopically identified in the laboratory, hydrogenated nitrogen (HN2) is thought to be an important species in combustion chemistry. The classical barrier height (10.6 +/- 0.2 kcal mol(-1)) and exothermicity (3.6 +/- 0.2 kcal mol(-1)) for the HN2 -> N-2+H reaction are predicted by high level ab initio quantum mechanical methods [up to CCSDT(Q)]. Total energies are extrapolated to the complete basis set limit applying the focal point analysis. Zero-point vibrational energies are computed...
Kinetics of crude oil combustion
Kök, Mustafa Verşan (Springer Science and Business Media LLC, 2006-02-01)
In this research, thermal characterization and kinetics of Karakus crude oil in the presence of limestone matrix is investigated. Thermogravimetry (TG/DTG) is used to characterize the crude oil in the temperature range of 20-900 degrees C, at 10 degrees C min(-1) heating rate using air flow rate of 20 mL min(-1). In combustion with air, three distinct reaction regions were identified known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). Five different kinetic m...
Citation Formats
A. Akdağ and S. D. Worley, “Mechanism of formation of biocidal imidazolidin-4-one derivatives: An ab initio density-functional theory,” JOURNAL OF PHYSICAL CHEMISTRY A, pp. 7621–7627, 2006, Accessed: 00, 2020. [Online]. Available: