Computational study of optical properties, and enantioselective synthesis of di-substituted esters of hydantoic and thiohydantoic acids

  • Hiwa Omer Ahmad Department of Pharmaceutical Chemistry, College of Pharmacy, Hawler Medical University. Hawler, Kurdistan Region, Iraq
Keywords: Density functional theory calculations; Energy, Molecular electrostatic potential, hydantoic acids.

Abstract

     The title compounds with different optically active substituted ester of hydantoic and thiohydantoic were synthesized by the reaction of corresponding enantio-pure amino acids methyl ester hydrochloride with phenylisocyanate/thiocyanate in the presence of triethylamine. The duration of reaction was limited to avoid racemisation and produce high enantio-enriched compounds. Low values of ELUMO-HOMO gap 0.14, 0.16, 0.15, 0.15, and 0.10 eV were observed for compounds 1, 2, 3, 4, and 5, respectively indicate soft, and high reactivity compounds. Values of ELUMO-HOMO gap also show that the compounds can easily decompose spontaneously to their elements. The order of synthesized compounds based on increasing reactivity depends on LUMO-HOMO energy gap represent as follows; 5>1>3, 4>2. Thermodynamic energies have been calculated for synthesized compounds including Enthalpy and Gibbs free energy.

References

ABDALLAH, H. 2019. Theoretical study for the inhibition ability of some bioactive imidazole derivatives against the Middle-East respiratory syndrome corona virus (MERS-Co). ZANCO Journal of Pure and Applied Sciences, 31, 71-78.
ABDULLAH, B. J., OMAR, M. S. & JIANG, Q. J. 2016. Grüneisen Parameter and Its Related Thermodynamic Parameters Dependence on Size of Si Nanoparticles. ZANCO Journal of Pure and Applied Sciences, 28, 126-132.
BALLARD, A., AHMAD, H. O., NARDUOLO, S., ROSA, L., CHAND, N., COSGROVE, D. A., VARKONYI, P., ASAAD, N., TOMASI, S. & BUURMA, N. J. 2018. Quantitative prediction of rate constants for aqueous racemization to avoid pointless stereoselective syntheses. Angewandte Chemie, 130, 994-997.
BALLARD, A., NARDUOLO, S., AHMAD, H. O., COSGROVE, D. A., LEACH, A. G. & BUURMA, N. J. 2019. The problem of racemization in drug discovery and tools to predict it. Expert opinion on drug discovery, 14, 527-539.
BECKE, A. D. 1993. Density‐functional thermochemistry. III. The role of exact exchange. The Journal of chemical physics, 98, 5648-5652.
CHONG, D., GRITSENKO, O. & BAERENDS, E. 2002. Interpretation of the Kohn–Sham orbital energies as approximate vertical ionization potentials. The Journal of Chemical Physics, 116, 1760-1772.
FAREGHI‐ALAMDARI, R., ZANDI, F. & KESHAVARZ, M. H. 2015. A new model for prediction of one electron reduction potential of nitroaryl compounds. Zeitschrift für anorganische und allgemeine Chemie, 641, 2641-2648.
FRISCH, A., NIELSON, A. & HOLDER, A. 2000. Gaussview user manual. Gaussian Inc., Pittsburgh, PA, 556.
FRISCH, M. J., TRUCKS, G. W., SCHLEGEL, H. B., SCUSERIA, G. E., ROBB, M. A., CHEESEMAN, J. R., SCALMANI, G., BARONE, V., PETERSSON, G. A., NAKATSUJI, H., LI, X., CARICATO, M., MARENICH, A. V., BLOINO, J., JANESKO, B. G., GOMPERTS, R., MENNUCCI, B., HRATCHIAN, H. P., ORTIZ, J. V., IZMAYLOV, A. F., SONNENBERG, J. L., WILLIAMS, DING, F., LIPPARINI, F., EGIDI, F., GOINGS, J., PENG, B., PETRONE, A., HENDERSON, T., RANASINGHE, D., ZAKRZEWSKI, V. G., GAO, J., REGA, N., ZHENG, G., LIANG, W., HADA, M., EHARA, M., TOYOTA, K., FUKUDA, R., HASEGAWA, J., ISHIDA, M., NAKAJIMA, T., HONDA, Y., KITAO, O., NAKAI, H., VREVEN, T., THROSSELL, K., MONTGOMERY JR., J. A., PERALTA, J. E., OGLIARO, F., BEARPARK, M. J., HEYD, J. J., BROTHERS, E. N., KUDIN, K. N., STAROVEROV, V. N., KEITH, T. A., KOBAYASHI, R., NORMAND, J., RAGHAVACHARI, K., RENDELL, A. P., BURANT, J. C., IYENGAR, S. S., TOMASI, J., COSSI, M., MILLAM, J. M., KLENE, M., ADAMO, C., CAMMI, R., OCHTERSKI, J. W., MARTIN, R. L., MOROKUMA, K., FARKAS, O., FORESMAN, J. B. & FOX, D. J. 2016. Gaussian 16 Rev. B.01. Wallingford, CT.
GALVÁN, J. E., GIL, D. M., LANÚS, H. E. & ALTABEF, A. B. 2015. Theoretical study on the molecular structure and vibrational properties, NBO and HOMO–LUMO analysis of the POX3 (X= F, Cl, Br, I) series of molecules. Journal of Molecular Structure, 1081, 536-542.
JAWHAR, Z. S., AHMAD, H. O., HAYDAR, A. A., ABDULLAH, H. A. & MAHAMAD, S. A. 2018. One-Pot Synthesis, Pharmacological Evaluation, Docking Study, and DFT Calculations for Selected Imidazolidine-2, 4-Diones. Science Journal of University of Zakho, 6, 150-154.
KUBINYI, H., FOLKERS, G. & MARTIN, Y. C. 2006. 3D QSAR in drug design: recent advances, Springer Science & Business Media.
LOMBARDINO, J. G. & GERBER, C. F. 1964. Preparation and hypoglycemic activity of some 3, 5-disubstituted hydantoins. Journal of Medicinal chemistry, 7, 97-101.
MORO, S., BACILIERI, M., FERRARI, C. & SPALLUTO, G. 2005. Autocorrelation of molecular electrostatic potential surface properties combined with partial least squares analysis as alternative attractive tool to generate ligand-based 3D-QSARs. Current drug discovery technologies, 2, 13-21.
RAO, Y. S., PRASAD, M., SRI, N. U. & VEERAIAH, V. 2016. Vibrational (FT-IR, FT-Raman) and UV–Visible spectroscopic studies, HOMO–LUMO, NBO, NLO and MEP analysis of Benzyl (imino (1H-pyrazol-1-yl) methyl) carbamate using DFT calculaions. Journal of Molecular Structure, 1108, 567-582.
ROCHA, M., DI SANTO, A., ARIAS, J. M., GIL, D. M. & ALTABEF, A. B. 2015. Ab-initio and DFT calculations on molecular structure, NBO, HOMO–LUMO study and a new vibrational analysis of 4-(dimethylamino) benzaldehyde. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 136, 635-643.
SCROCCO, E. & TOMASI, J. 1978. Electronic molecular structure, reactivity and intermolecular forces: an euristic interpretation by means of electrostatic molecular potentials. Advances in quantum chemistry. Elsevier.
SHANKAR, R., SENTHILKUMAR, K. & KOLANDAIVEL, P. 2009. Calculation of ionization potential and chemical hardness: a comparative study of different methods. International Journal of Quantum Chemistry, 109, 764-771.
WARE, E. 1950. The chemistry of the hydantoins. Chemical Reviews, 46, 403-470.
Published
2020-02-25
How to Cite
Ahmad, H. (2020) “Computational study of optical properties, and enantioselective synthesis of di-substituted esters of hydantoic and thiohydantoic acids”, Zanco Journal of Pure and Applied Sciences, 32(1), pp. 75-94. doi: 10.21271/zjpas.32.1.9.
Section
Biology and Medical Researches