Molecular structure, vibration properties and quantum chemical calculations of 4-(chloromethyl)-7-methoxycoumarin and 4-(chloromethyl)-7-methyl-coumarin

Yıl 2016, Cilt: 2 Sayı: 2, 48 - 55, 15.08.2016

Feride Akman Kamuran Sarac

https://doi.org/10.20863/nsd.78025

Öz

Objective: This study presents the quantum chemical calculations of 4-(Chloromethy)-7-methoxycoumarin (1) and 4-(Chloromethy)-7-methylcoumarin (2).

Material and Methods: The solid phase FT-IR spectra of compounds 1 and 2 have been recorded in the region 4000–500 cm^-1. The molecular geometry, vibrational frequency of compounds 1 and 2 in the ground state have been calculated by utilizing the density functional method (DFT/B3LYP) with the 6-311G+ (d, p) basis set. The calculated vibrational frequencies are compared with experimental obtained by FT-IR spectra. On the other hand, frontier molecular orbitals (FMOs) and molecular electrostatic potentials (MEP) of compounds 1 and 2 were calculated at the B3LYP/6-311G+ (d, p) level of theory.

Results: With the aid of the theoretical calculations, the vibrational frequencies are precisely assigned to their molecular structure.

Conclusion: The theoretical and experimental results support each other.

Anahtar Kelimeler

4-(Chloromethy)-7-methoxycoumarin and 4-(Chloromethy)-7-methylcoumarin, FT-IR spectra; DFT; Vibrational frequencies

Molecular structure, vibration properties and quantum chemical calculations of 4-(chloromethyl)-7-methoxycoumarin and 4-(chloromethyl)- 7-methyl-coumarin

Öz

Kaynakça

• Sarıkaya EK, Dereli Ö, Erdoğdu Y, Güllüoğlu MT. Molecular structure and vibrational spectra of 7-Ethoxycoumarin by density functional method. Journal of Molecular Structure. 2013;1049: 220-226.
• Koparir M, Orek C, Koparir P, Sarac K. Synthesis, experimental, theoretical characterization and biological activities of 4-ethyl-5-(2-hydroxyphenyl)-2H-1, 2, 4-triazole-3 (4H)-thione. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2013; 105: 522-531.
• Kumar S, Saini A, Sandhu JS. LiBr-Mediated, solvent free von Pechmann reaction: facile and efficient method for the synthesis of 2H-chromen-2-ones. Arkivoc. 2007;15: 18-23.
• Mannekutla JR, Mulimani BG, Inamdar SR. Solvent effect on absorption and fluorescence spectra of coumarin laser dyes: evaluation of ground and excited state dipole moments. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2008; 69(2): 419-426.
• Christie RM, Lui CH. Studies of fluorescent dyes: part 1. An investigation of the electronic spectral properties of substituted coumarins.Dyes and Pigments. 1999; 42(1): 85-93.
• Von Pechmann H, Duisberg C. Ueber die verbindungen der phenole mit acetessigäther. Berichte der deutschen chemischen Gesellschaft. 1883; 16(2):2119-2128.
• Adams R, Bockstahler TE. Preparation and reactions of o-hydroxycinnamic acids and esters. Journal of the American Chemical Society. 1952; 74(21): 5346-5348.
• Johnson JR. The Perkin reaction and related reactions. Organic Reactions.1942.
• Shriner RL. The reformatsky reaction, Organic reactions. 1942.
• Yavari I, Hekmat-Shoar R, Zonouzi A. A new and efficient route to 4-carboxymethylcoumarins mediated by vinyltriphenylphosphonium salt.Tetrahedron Letters. 1998; 39(16): 2391-2392.
• Palafox MA, Rastogi VK, Tanwar RP, Mittal L. Vibrational frequencies and structure of 2-thiouracil by Hartree–Fock, post-Hartree–Fock and density functional methods. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2003; 59(11): 2473-2486.
• Ten GN, Nechaev VV, Pankratov AN, Berezin VI, Baranov VI. Effect of hydrogen bonding on the structure and vibrational spectra of the complementary pairs of nucleic acid bases. II. adenine-thymine. Journal of Structural Chemistry. 2010; 51(5): 854-861.
• Szczesniak M, Nowak MJ, Szczepaniak K, Chin S, Scott I, Person WB. Matrix isolation studies of nucleic acid constituents—III. 1-Methyluracil, 3-methyluracil and 1, 3-dimethyluracil monomers. Spectrochimica Acta Part A: Molecular Spectroscopy. 1985; 41(1): 223-235.
• Çırak Ç, Koç N. Molecular structure and effects of intermolecular hydrogen bonding on the vibrational spectrum of trifluorothymine, an antitumor and antiviral agent. Journal of molecular modeling. 2012; 18(9): 4453-4464.
• Mohan S, Sundaraganesan N, Mink J. FTIR and Raman studies on benzimidazole. Spectrochimica Acta Part A: Molecular Spectroscopy. 1991; 47(8): 1111-1115.
• Palafox MA, Tardajos G, Guerrero-Martínez A, Rastogi VK, Mishra D, Ojha SP, Kiefer W. FT-IR, FT-Raman spectra, density functional computations of the vibrational spectra and molecular geometry of biomolecule 5-aminouracil. Chemical Physics. 2007; 340(1): 17-31.
• Jamróz MH, Dobrowolski JC, Brzozowski R. Vibrational modes of 2, 6-, 2, 7-, and 2, 3-diisopropylnaphthalene. A DFT study. Journal of molecular structure. 2006; 787(1): 172-183.
• Singh JS. FTIR and Raman spectra and fundamental frequencies of biomolecule: 5-methyluracil (thymine). Journal of Molecular Structure. 2008; 876(1): 127-133.
• Çırak Ç, Sert Y, Ucun F. Experimental and computational study on molecular structure and vibrational analysis of a modified biomolecule: 5-Bromo-2′-deoxyuridine. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2012; 92: 406-414.
• Akman F. Spectroscopic investigation, HOMO–LUMO energies, natural bond orbital (NBO) analysis and thermodynamic properties of two-armed macroinitiator containing coumarin with DFT quantum chemical calculations.Canadian Journal of Physics. 2016; 94(6): 583-593.
• Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, et. al. Gaussian, Inc., Wallingford CT, 2010.
• Dennington R, Keith T, Millam J. GaussView, Version 5, Semichem Inc., Shawnee Mission KS, 2010.
• Schlegel HB. Optimization of equilibrium geometries and transition structures. Journal of Computational Chemistry. 1982; 3(2): 214-218.
• Sarıkaya EK, Dereli Ö. Molecular structure and vibrational spectra of 7-Methoxy-4-methylcoumarin by density functional method. Journal of Molecular Structure. 2013 ;1052: 214-220.
• Koparir M, Orek C, Alayunt NO, Parlak AE, Koparir P, Sarac K, Cankaya N. Synthesis, Structure Investigation, Spectral Characteristics and Biological Activitie of 4-Benzyl-3-(2-Hydroxyphenyl)-1H-1, 2, 4-Triazole-5 (4H)-Thione. Communications in Computational Chemistry. 2013; 1: 244-268.
• Raj RK, Gunasekaran S, Gnanasambandan T, Seshadri S. Combined spectroscopic and DFT studies on 6-bromo-4-chloro-3-formyl coumarin. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2015; 139: 505-514.
• Sagdinc S, Pir H. Spectroscopic and DFT studies of flurbiprofen as dimer and its Cu (II) and Hg (II) complexes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2009; 73(1): 181-194.
• Fleming I. Frontier Orbitals and Organic Chemical Reactions, John Wiley and Sons, New York, 1976.
• Muthu S, Prasath M, Balaji RA. Experimental and theoretical investigations of spectroscopic properties of 8-chloro-1-methyl-6-phenyl-4H-[1, 2, 4] triazolo [4, 3-a][1, 4] benzodiazepine. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2013; 106: 129-145.
• Scrocco E, Tomasi J. The electrostatic molecular potential as a tool for the interpretation of molecular properties. In New concepts II (pp. 95-170). Springer Berlin Heidelberg.1973.