Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Molecular structure and vibrational spectra of 2-Ethoxymethyl-6-ethyl-2,3,4,5-tetrahydro-1,2,4-triazine-3,5-dione, a potential chemotherapeutic agent, by density functional methods
Graphical abstract
Introduction
1,2,4-Triazine-3,5(2H,4H)-diones (6-azauracils) represent an important class of biologically-active heterocyclic compounds. Several 1,2,4-triazine-3,5-diones showed antiviral [1], [2], [3], antimicrobial [4], [5], [6], [7], anti-inflammatory activities [8], [9], antimalarial [10], anticancer [11], [12], [13], [14] and antiulcer [15] activities. The title compound was synthesized as a potential antimicrobial agent. It was prepared by treatment of silylated 6-ethyl-1,2,4-triazine-3,5(2H,4H)-dione with chloroethyl ether in the presence of cesium iodide [7]. 1,2,4-triazine molecule is an aza-analogue of pyrimidine. 1,2,4-triazine and its derivatives belong to an important class of hetero aromatic compounds and they exhibit various interesting biochemical properties [16], [17]. Derivatives of 1,2,4-triazine present important core in many natural [18], [19] and synthetic [20], [21] biologically active compounds [22]. These hetero cycles easily undergo different substitution reactions and ring transformation [23], [24] that makes them convenient precursors for the synthesis of other hetero aromatic compounds. The single crystal XRD study of the title compound was reported by El-Brollosy et al. [25]. The present study describes the electronic properties and vibrational spectra of the title compound (molecular formula C8H13N3O3), with the hope that the results of present study would be helpful in future synthesis of more potent chemotherapeutic analogues. The energies, degrees of hybridization, populations of the lone electron pairs of oxygen, energies of their interaction with the anti-bonding orbital of the benzene ring and the electron density distributions and E(2) energies have been calculated by NBO analysis using DFT method to give clear evidence of stabilization originating from the hyper conjugation of various intra-molecular interactions. There has been growing interest in using organic materials for nonlinear optical devices, functioning as second harmonic generators, frequency converters, electro optical modulators etc., because of the large second order electric susceptibilities of organic materials. Since the second order electric susceptibility is related to first hyperpolarizability the search for organic chromophores with large first hyperpolarizability is fully justified.
Section snippets
Experimental details
The title compound was synthesized according to the reported protocol [7] and was re-crystallized from ethanol. The 1,2,4-traizine ring of the title compound C8H13N3O3 is nearly planar. The imino group is hydrogen bond donor to the exocylic O atom at the 5-position of an adjacent molecule, the NH⋯O hydrogen bond generating a chain parallel to the b axis [25]. The FT-IR spectrum (Fig. 1) was recorded using KBr pellets on a DR/JASCO FT-IR 6300 spectrometer, with a spectral resolution 4 cm−1 and
Computational details
Calculations of the title compound were carried out with Gaussian09 software [26] program using B3PW91/6-31G(d)(6D,7F) and B3LYP/6-31G(d)(6D,7F) basis sets to predict the molecular structure and vibrational wavenumbers. Calculations were carried out with Becke’s three parameter hybrid model using the Lee–Yang–Parr correlation functional (B3LYP) method. Molecular geometries were fully optimized by Berny’s optimization algorithm using redundant internal coordinates. Harmonic vibrational
IR and Raman spectra
The calculated (scaled) wavenumbers and observed IR, Raman bands and assignments are given in Table 2. The stretching mode of NH group is generally rive rise to bands [30], [31] in the range 3500–3300 cm−1. For the title compound the NH stretching mode is observed at 3425 cm−1 in the IR spectrum, 3445 cm−1 in the Raman spectrum and theoretical value is 3451 cm−1 (B3LYP). NH group show bands at 1510–1500, 1450–1250 and 740–730 cm−1 [32]. According to literature, if NH is a part of a closed ring [33],
Conclusion
FT-IR, FT-Raman and DFT quantum chemical calculations studies were performed on 2-Ethoxymethyl-6-ethyl-2,3,4,5-tetrahydro-1,2,4-triazine-3,5-dione, in order to identify the structure and vibrational features. On the basis of experimental results and potential energy distribution calculations, assignments of all the fundamental vibrational wavenumbers were done. A good correlation between the scaled wavenumbers and observed values was obtained for the title molecule. The NBO analysis shows
Acknowledgements
The authors would like to extend their sincere appreciation to the Deanship of Scientific Research at King Saud University for funding this work through the Research Group Project No. RGP-VPP-274. The authors are thankful to University of Antwerp for access to the University’s CalcUA supercomputer cluster.
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