DFT CALCULATIONS OF BENZOISOXAZOLE DERIVATIVES

Year 2019, Volume: 61 Issue: 1, 31 - 54, 31.12.2019

Ezgi Özen Melike Kalkan Pervin Ünal Civcir

Abstract

In this work, we carried out theoretical calculations to determine the structureactivity relationship and the properties of two benzoisoxazole derivatives. For the quantum chemical calculations, the Density Functional Theory (DFT) with B3LYP (Becke threeparameter hybrid correlation functional combined with Lee–Yang–Parr correlation functional) and 6-311+G(d,p) basis set were employed both in the gas phase and in different solvents such as toluene, chloroform, THF, DCM, acetone, DMSO. The CPCM (conductorlike polarizable continuum) solvation model was also used to compute condensed-phase energies in solvent systems. The structural parameters (bond lengths, bond angles, and dihedral angles), energetics (the total energies, the zero-point vibrational energies, the frontier orbital energies (EHOMO, ELUMO), and the bandgap energies) and the spectroscopic characteristics (UV, IR, 1H-NMR, and 13C-NMR) of the target molecules were also determined. The results of the calculations were compared with experimental values for molecule 1, which exists in literature. The calculated geometries (bond length, bond angle and dihedral angle) were in a good agreement with the experimental data. In the case of IR frequencies, the scaled calculated frequencies agreed reasonably well with the experimental results. Moreover, there is a good correlation between experimental and calculated proton signals (R² = 0.9769) and carbon signals (R² = 0.9972) of molecule 1.

Keywords

Benzoisoxazoles, Density Functional Theory, IR, UV, NMR

References

• K. Ha, H. S. Lim and H. J. Kim, 5-(4-Chlorophenyl)-6-isopropyl-5,6-dihydro-4Hpyrrolo[3,4-c]isoxazole. Acta Crystallographica, E66 (2010) o2483.
• K. V. N. Raju, M. Krishnaiah, N. J. Kumar and S. N. Rao, Structure conformation of 4-(4-methoxyphenyl)-5-phenyl isoxazole. Acta Crystallographica, A58 (2002) c128.
• M. Krishnaiah, R. R. Kumar, T. Oo and P. Kaung, 4-(4-Chlorophenyl)-5-phenylisoxazole. Acta Crystallographica, E65 (2009) o2324.
• H. Hasegawa, Utilization of zonisamide inpatients with chronic pain orepilepsy refractory to other treatments: a retrospective, open label, uncontrolled study in a VA hospital. Current Medical Research and Opinion, 20/5 (2004) 577-580.
• Y. Masuda, Y. Utsui, Y. Sharashi, T. Karasawa, K. Yoshida and M. Shimizu, Relationships between plasma concentrations of diphenylhydantoin, phenobarbital, carbamazepine, and 3-sulfamoylmethyl-1,2-benzoisoxazole (AD-810), a new anticonvulsant agent, and their anticonvulsant or neurotoxic effects in experimental animals. Epilepsia, 20/6 (1979) 623-633.
• H. Uno, M. Kurukova, Y. Masuda and H. Nishimura, Studies on 3-substituted 1,2-benzoisoxazole derivatives. 6. Syntheses of 3-(sulfamoylmethyl)-1,2-benzoisoxazole derivatives and their anticonvulsant activities. Journal of Medicinal Chemistry, 22/2 (1979) 180-183.
• G. V. Bossche, Y. G. Gelders and S. L. Heylen, Development of new antipsychotic drugs. Acta psiquiátrica y psicológica de América Latina, 36 (1990) 13-25.
• M. Shimizu, T. Karasawa, M. Masuda and M. Oka, 1,2-Benzoisoxazole-3-acetamidoxime hydrochloride, a new psychotropic agent. Experientia, 30/4 (1974) 405-405.
• M. Jain and C. H. Kwon, 1,2-Benzoisoxazole Phosphorodiamidates as Novel Anticancer Prodrugs Requiring Bioreductive Activation. Journal of Medicinal Chemistry, 46/25 (2003) 5428-5436.
• K. A. Thakar and B. M. Bhawal, Synthesis and Antimicrobial screening of amino-1, 2-Benzoisoxazoles and sulphanilamido-1, 2 benzoisoxazoles. Current Science, 47/24 (1978) 950-952.
• V. R. Arava, G. Laxminarasimhulu, U. B. R. Siripalli and P. K. Dubey, An efficient synthesis of 3-chloromethyl-1,2-benzoisoxazoles via modified Boekelheide rearrangement. Indian Journal of Chemistry, 50B/1 (2011) 119-125.
• W. Kohn and L.J. Sham, Self-Consistent Equations Including Exchange and Correlation Effects. Physical Review, 140A (1965) 1133–1138.
• M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato M, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox (2009) Gaussian 09, Revision D.01. Gaussian, Inc., Wallingford CT. [14] R. Dennington, T. Keith, and J. Millam, (2009) GaussView, Version 5.0.8. [15] A. D. Becke, Density-functional exchange-energy approximation with correct asymptotic behavior. Physical Review A, 38 (1988) 3098–3100.
• C. Lee, W. Yang and R. G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical Review B, 37 (1988) 785–789.
• K. Raghavachari, J. S. Binkley, R. Seeger and J. A. Pople, Self consistent molecular orbital methods. XX. A basis set for correlated wave functions. Journal of Chemical Physics, 72 (1980) 650-654.
• P. Ü. Civcir, G. Kurtay and K. Sarıkavak, Experimental and theoretical investigation of new furan and thiophene derivatives containing oxazole, isoxazole, or isothiazole subunits. Structural Chemistry, 28/3 (2017) 773–790.
• M. Kayalvizhi, G. Vasuki, A. Veerareddy and G. Laxminarasimha, 3-Chloromethyl-6,7-dimethyl-1,2-benzoxazole. Acta Crystallographica Section E, 68/10 (2012) o3008-o3008.
• I. Fleming, Frontier Orbitals and Organic Chemical Reactions. Wiley, London, 1976.
• R. E. Stratmann, G. E. Scuseria and M. J. Frisch, An efficient implementation of timedependent density-functional theory for the calculation of excitation energies of large molecules. Journal of Chemical Physics, 109/19 (1998) 8218-8224.
• J. P. Merrick, D. Moran and L. Radom, An Evaluation of Harmonic Vibrational Frequency Scale Factors. Journal of Physical Chemistry A, 111/45 (2007) 11683–11700.
• E. Erdik, Organik Kimyada Spektroskopik Yöntemler. Gazi Kitabevi, Ankara, 2015.
• K. Wolinski, J. F. Hinton and P. Pulay, Efficient implementation of the gaugeindependent atomic orbital method for NMR chemical shift calculations. Journal of the American Chemical Society, 112/23 (1990) 8251–8260.
• R. Ditchfield, Self-consistent perturbation theory of diamagnetism. Molecular Physics, 27/4 (1974) 789–807.