Serpil ERYILMAZ, Kerem MESCİ, Melek GÜL, Ersin İNKAYA

THE INVESTIGATION OF SPECTROSCOPIC AND THEORETICAL METHODS OF BISISOXAOLINE DERIVATIVE OF NORBORNADIEN

In this study, the synthesis of bisisoxaoline derivative of norbornadien from heterocyclic compounds was performed via 1,3-dipolar cycloaddition reaction, the structural properties of derivative characterized by spectroscopic analysis such as FT-IR, 1H-NMR, 13C-NMR, UV-Vis and the single-crystal X-ray diffraction technique. The 3,7-bis(4-(tert-butyl)phenyl)-3a,4,4a,7a,8,8a-hexahydro-4,8-methanobenzo[1,2-d:4,5-d’]diisoxazole compound was optimized using Density Functional Theory (DFT/B3LYP) method with 6-311G(d,p) basis set in the ground state and the geometric parameters compared with single-crystal X-ray diffraction technique. The compound crystallizes in the monoclinic space group C2/c with a = 20.634(4) Å, b = 11.179(2) Å, c = 11.0690(17) Å and Z = 4 unit cell parameters. Also, the spectral results were examined with calculated vibrational frequencies, 1H-NMR, 13C-NMR chemical shift values and absorption wavelengths, theoretically. The energetic behaviour of the compound in different solvent media was examined with TD-DFT/B3LYP method and 6-311G(d,p) basis set using the Conductor Polarizable Continuum Model (CPCM). The frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP) and electronic structure parameters (dipole moment, electronegativity, chemical hardness-softness, ionization potential, electron affinity, etc.) were examined to get information about the chemical stability of the structure.

Keywords:

Bisisoxaoline, DFT, Single Crystal X-ray, FT-IR,

PDF

___

[1] a)Padwa A. 1,3-Dipolar Cycloaddition Chemistry II. 3rd. Ed. New York, NY, USA: Wiley Press, 1984.
b)Padwa A. Synthetic Application of 1,3-dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products. 3rd. Ed. New York NY, USA: Wiley Press, 2001.
[2] a)Kaur K, Kumar V, Sharma AK, Gupta GK. Isoxazoline containing natural products as anticancer agents: A Review. Eur J Med Chem. 2014; 77:121-33.
b)Pekka KP, Tuomas O, Mikael P, Jorma JP, Janne AI, Reino L, Juha TP. Design, Synthesis, and Biological Evaluation of Nonsteroidal Cycloalkane[d]isoxazole-Containing Androgen Receptor Modulators. J. Med Chem 2012; 55 (14): 6316–6327.
[3] Bolvig T, Larsson OM, Pickering DS, Nelson N, Falch E, Krogsgaard-Larsen P, Schousboe A. Action of bicyclic isoxazole GABA analogues on GABA transporters and its relation to anticonvulsant activity. Eur J Pharmacol. 1999; 375(1-3):367-74.
[4] Tangallapally RP, Yendapally R, Daniels AJ, Lee REB, Lee RE. Nitrofurans as Novel Anti-tuberculosis Agents: Identification, Development and Evaluation. Curr Top Med Chem 2007; 7:509–526
[5] Rakesh DS, Lee RB, Tangallapally RP, Lee RE.Synthesis, optimization and structure–activity relationships of 3,5-disubstituted isoxazolines as new anti-tuberculosis agents. Eur J Med Chem 2009; 44:460–472.
[6] Werner A. Über die Raumliche Anordnung der Atome in Stick Stoff Haltisen Molekülen. Berichte 1890; 23:11-30.
[7] a)Tranmer GK, MolybdenumWT. Mediated Cleavage Reactions of Isoxazoline Rings Fused in Bicyclic Frameworks. Org. Lett 2002; 4 (23): 4101–4104
b)Murphy JJ, Hamilton JG, Paton R M.Synthesis and ring opening metathesis polymerisation of isoxazolino and isoxazolidino-norbornenes. Polymer 2006; 47 (10): 3292-3297.
[8] Eryılmaz S, Gül M, İnkaya E, İdil Ö, Özdemir Namık. Synthesis, Crystal Structure Analysis, Spectral Characterization, Quantum Chemical Calculations, Antioxidant and Antimicrobial Activity of 3-(4-chlorophenyl)-3a,4,7,7a-tetrahydro-4,7-methanobenzo[d]isoxazole. J Mol Struct 2016; 1122: 219-233.
[9] Stoe&Cie, X-AREA (Version 1.18), Stoe&Cie GmbH, Darmstadt, Germany, 2002.
[10] Sheldrick GM. SHELXS-97. Program for the Solution of Crystal Structures. University of Gottingen. 1997.
[11] Farrugia LJ. J Appl Crystallogr 1999; 30: 837-838.
[12] Sheldrick GM. Acta Crystallogr 2015; C71: 3-8.
[13] Stoe&Cie, X-RED (Version 1.04), Stoe&Cie GmbH, Darmstadt, Germany, 2002.
[14] Spek AL. Acta Crystallogr D 2009; 65: 148-155.
[15] Frisch, M. J. et al. Gaussian 09, Revision E.01, Gaussian, Inc., Wallingford CT, 2009.
[16] Dennington, Roy; Keith, Todd; Millam, John. GaussView, Version 5, Semichem Inc., Shawnee Mission, KS, 2009.
[17] a)Becke AD.Density-functional exchange-energy approximation with correct asymptotic behavior. J Chem Phys 1988; 38: 3098-3100.
b)Becke AD.Density-Functional Thermochemistry. I. The Effect of the Exchange-Only Gradient Correction. J Chem Phys1992; 96: 2155-2160.
c)Becke AD.Density functional thermochemistry III. The role of exact exchange. J Chem Phys1993; 98: 5648-5652.
[18] Ditchfield R,Hehre WJ, Pople JA.Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules
J Chem Phys1971; 54: 724-728.
[19] Lee C, Yang CW, Parr R.Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev1988; 37: 785–789.
[20] Merrick JP, Moran D, Radom L. An Evaluation of Harmonic Vibrational Frequency Scale Factors. J Phys Chem A 2007; 111: 11683-11700.
[21] a)London F.Théorie quantique des courants interatomiques dans les combinaisons aromatiques. J Phys Radium 1937; 8: 397-409.
b)McWeeny R. Perturbation Theory for the Fock-Dirac Density Matrix
Phys Rev 1962; 126: 1028.
c)Ditchfield R. Self-consistent perturbation theory of diamagnetism.Mol Phys 1974; 27: 789-807.
d)Wolinski K, Hilton JF, Pulay P. Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations. J Am Chem Soc 1990; 112: 8251-8260.
e)Cheeseman JR, Trucks GW, Keith TA, Frisch MJ. A comparison of models for calculating nuclear magnetic resonance shielding tensors. J Chem Phys 1996; 104: 5497-5509.
[22] Barone V, Cossi M. Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model. J Phys Chem A 1998; 102: 1995-2001.
[23] Jin YX, Zhong AG, Ge CH, Pan FY, Yang JG, Wu Y, Xie M, Feng HW. A novel difunctional acylhydrazone with isoxazole and furan heterocycles: Syntheses, structure, spectroscopic properties, antibacterial activities and theoretical studies of (E)-N0 -(furan-2-ylmethylene)-5-methylisoxazole-4- carbohydrazide. J Mol Struct 2012; 1010: 190-196.
[24] Tamer Ö, Avcı BS, Avcı D, Nebioglu M, Atalay Y, Çoşut B.Synthesis, molecular structure, spectral analysis and nonlinear optical studies on 4-(4-bromophenyl)-1-tert-butyl-3-methyl-1H-pyrazol-5- amine: A combined experimental and DFT approach.J Mol Struct 2016; 1106: 89-97.
[25] Dege N, Senyüz N, Batı H, Günay N, Avcı D, Tamer O, Atalay Y. The synthesis, characterization and theoretical study on nicotinic acid [1-(2,3-dihydroxyphenyl)methylidene]hydrazide. Spectrochim Acta A 2014; 120: 323-331.
[26] Eryılmaz S, Gül M, İnkaya E, Taş M. Isoxazole Derivatives of Alpha-pinene Isomers: Synthesis, Crystal Structure, Spectroscopic Characterization (FT-IR/NMR/GC-MS) and DFT Studies. J Mol Struct 2016; 1108: 209-222.
[27] Mohan J. Organic Spectroscopy:Principles and Applications. 2nd Ed. Harrow, UK: Alpha Science, 2004.
[28] Erdik E. Organik Kimyada Spektroskopik Yöntemler. 5. Baskı. Ankara, Türkiye: Gazi Kitabevi, 2008.
[29] Stuart BH. Infrared Spectroscopy: Fundamentals and Applications. 1st Ed. Chichester, England:Wiley 2004.
[30] Zhang XH, Zhan YH, Chen D, Wang F, Wang LY. Merocyanine dyes containing an isoxazolone nucleus: Synthesis, X-ray crystal structures, spectroscopic properties and DFT studies. Dyes and Pigm 2012; 93: 1408-1415.
[31] Jin RY, Sun X H, Liu YF, Long W, Chen B, Shen SQ, Ma HX. Synthesis, crystal structure, biological activity and theoretical calculations of novel isoxazole derivatives. Spectrochim Acta A 2016; 152: 226-232.
[32] Kalinowski HO, Berger S, Braun S. Carbon-13 NMR Spectroscopy. 1st ed. Chichester, UK John Wiley&Sons, 1988.
[33] Pihlaja K, Kleinpeter E. Carbon-13 Chemical Shifts in Structural and Stereochemical Analysis. 1st ed. USA: Wiley-VCH Publishers, 1994.
[34] Balcı M. Nükleer Manyetik Rezonans Spektroskopisi. 2. Baskı. Ankara, Türkiye:ODTÜ Yayıncılık, 2004.
[35] İnkaya E, Günnaz S, Özdemir N, Dayan O, Dinçer M, Çetinkaya B. Synthesis, spectroscopic characterization, X-ray structure and DFT studies on 2,6-bis(1-benzyl-1H-benzo[d]imidazol-2-yl)pyridine. Spectr Acta Part A 2013; 103: 255–263.
[36] İnkaya E, Dinçer M, Ekici Ö, Çukurovalı A. N′-(2-methoxy-benzylidene)-N-[4-(3-methyl-3-phenyl-cyclobutyl)-thiazol-2-yl]-chloro-acetic hydrazide: X-ray structure, spectroscopic characterization and DFT studies. J Mol Struct 2012; 1026:117-126.
[37] Fleming I. Frontier Orbitals and Organic Chemical Reactions. London, UK:Wiley, 1976.
[38] Tarı GÖ, Gümüş S, Ağar E. Crystal structure, spectroscopic studies and quantum mechanical calculations of 2-[((3-iodo-4-methyl)phenylimino)methyl]-5-nitro thiophene. Spectromica Acta Part A 2015; 141: 119-127.
[39] Vijayaraj R,Subramanian V, Chattaraj PK. Comparison of Global Reactivity Descriptors Calculated Using Various Density Functionals: A QSAR Perspective. J Chem Theory Comput 2009; 5(10): 2744–2753.
[40] Padmanabhan J, Parthasarathi R, Elango M, Subramanian V, Krishnamoorthy BS, Gutierrez-Oliva S, Toro-Labbe A, Roy D R, Chattaraj PK. Multiphilic Descriptor for Chemical Reactivity and Selectivity. J. Phys. Chem. A 2007; 111: 9130-9138.
[41] a)Koopmans T. Physica 1. 1933; 104.
b)Vektariene A, Vektaris G. J Svoboda.A theoretical approach to the nucleophilic behavior of benzofused thieno[3,2-b]furans using DFT and HF based reactivity descriptors. ARKIVOC 2009; vii: 311-329.
[42] Mulliken RS. J Chem Phys 1934; 2: 782.
[43] a)Pearson RG.Hard and Soft Acids and Bases. J Am Chem Soc1963; 85:3533-3539
b)Pearson RG. Hard and soft acids and bases, HSAB, part 1: Fundamental principles.
J Chem Educ1968;45(9): 581.
c)Pearson RG. Maximum Chemical and Physical Hardness. J Chem Educ1999;2 (76): 267.
[44] Pearson RG. Absolute electronegativity and hardness correlated with molecular orbital theory. Pro Nat Acad Scie 1986; 83: 8440-8441.
[45] Parr RG, Pearson RG. Absolute hardness: companion parameter to absolute electronegativity.
J Am Chem Soc 1983;105: 7512-7516.
[46] Chattaraj PK, Sarkar U, Roy DR. Electrophilicity index. Chem Rev 2006; 106: 2065-2091
[47] İnkaya E, Dinçer M, Ekici Ö, Çukurovalı A. 1-(3-Methyl-3-mesityl)-cyclobutyl-2-(5-pyridin-4-yl-2H-[1,2,4]triazol-3-ylsulfanyl)-ethanone: X-ray structure, spectroscopic characterization and DFT studies. Spect Acta Part A 2013; 101: 218-227.

Eskişehir Technical University Journal of Science and Technology A - Applied Sciences and Engineering-Cover

ISSN: 2667-4211
Yayın Aralığı: Yılda 4 Sayı
Başlangıç: 2000
Yayıncı: Eskişehir Teknik Üniversitesi

Arşiv