Open Access

Experimental spectroscopic (FT-IR, FT-Raman, NMR) and DFT Studies of 7-methoxy- 4-bromomethyl coumarin

N. Prabavathi , n.prabavathi@yahoo.co.in
Department of Physics, Sri Sarada College for women (Autonomous), Salem, TN, India
N. Senthil Nayaki Department of Physics, Sri Sarada College for women (Autonomous), Salem, TN, India


J. Environ. Nanotechnol., Volume 3, No 2 (2014) pp. 108-121

https://doi.org/10.13074/jent.2014.03.142072

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Abstract

The vibrational fundamental modes of 7-methoxy- 4-bromomethylcoumarin (7BMC) have been analyzed by combining FTIR, FT-Raman and quantum chemical calculations. The structural parameters of the compound are determined from the optimized geometry by B3LYP method with 6-311++G (d, p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FTIR and FT-Raman spectra. 1H and 13C NMR spectra have been analyzed and 1H and 13C nuclear magnetic resonance chemical shifts are calculated using the gauge independent atomic orbital (GIAO) method. The theoretical UV–VIS spectrum of the compound and the electronic properties, such as HOMO (highest occupied molecular orbital) and LUMO (lowest occupied molecular orbital) energies were performed by time-dependent density functional theory (TD-DFT) approach. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule have been obtained by mapping electron density isosurface with molecular electrostatic potential (MESP).The change in electron density (ED) in the σ* antibonding orbitals and stabilization energies E (2) have been calculated by natural bond (NBO) analysis to give clear evidence of stabilization originating in the hyper conjugation of hydrogen–bonded interactions.

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Reference


Aihara, J., Reduced HOMO-LUMO Gap as an Index of Kinetic Stability for Polycyclic Aromatic Hydrocarbons, J. Phys. Chem. A., 103, 7487-7495 (1999). 

http://dx.doi.org/10.1021/jp990092i

Alekseev, S. M., Pomoinitskii, V. D., Sarycheva, I. K., Evstigneeva, R. P., Use of 4- bromomethyl-7-methoxycoumarin for the quantitative fluorometric analysis of prostaglandins, Pharmaceutical Chemistry Journal., 15(11),825-827(1981). 

http://dx.doi.org/10.1007/BF00760468 

Arjunan, V., Arushma Raj, Ravindran, P., Mohan, S., Structure-activity relations of 2- (methylthio)benzimidazole by FTIR,FT-Raman, NMR, DFT and conceptual DFT methods, Spectrochim. Acta., 118, 951-965(2014). 

http://dx.doi.org/10.1016/j.saa.2013.09.100

Arjunan, V., Sakiladevi, S., Marchewka, M. K., Mohan, S., FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin, Spectrchim. Acta., 109, 79-89(2013).

http://dx.doi.org/10.1016/j.saa.2013.01.100

Balachandran, V., Karunakaran, V., Quantum mechanical study of the structure and vibrational spectroscopic (FT-IR and FT-Raman), first-order hyperpolarizability, NBO and HOMO-LUMO studies of 4-bromo-3-nitroanisole, Spectrochim. Acta ,106, 284-298 (2013).

http://dx.doi.org/10.1016/j.saa.2012.12.070

Benito-Reyes-Trejo, Diana Guerra-Ramiez, Holber Zuleta-Prada, Rosa Santillan, Maria Elena Sanchez-Mendoza, Jesus Arrieta and Lino Reyes, Molecular Disorder in (-)-Encecanescin, Molecules, 19,4695-4707(2014).

http://dx.doi.org/10.3390/molecules19044695

Borges, F., Roleira, F., Milhazes, N., Santana, L., Uriarte, E., Simple coumarins and analogues in medicinal chemistry: occurrence, synthesis and biological activity, Curr. Med. Che., 12, 887-916(2005).

http://dx.doi.org/10.2174/0929867053507315

Elbert, W., Breitenbach, S., Neftel, A., Hahn, J., 4-methyl-7-methoxycoumarin as a fluorescent label for high-performance liquid chromatographic analysis of dicarboxylic acid, J. chromatogr., A, 328, 111-120(1985).

http://dx.doi.org/10.1016/S0021-9673(01)87382-9

El-Nahass, M.M., Kamel, M.A., El-Deeb, A.F., Atta, A.A., Huthaily, S.Y., Density functional theory (DFT) investigation of molecular structure and frontier molecular orbitals (FMOs) of P- N,N-dimethylaminobenzylidenemalononitrile (DBM), Spectrochim. Acta, 79, 1499-1504 (2011).

http://dx.doi.org/10.1016/j.saa.2011.05.006

Isa Sidir, Yadigar Gulseven Sidir, Erol Tasal, Cemil Ogretir, Ab initio Hartree-Fock and density functional theory inestigations on the conformational stability, molecular structure and vibrational spectra of 3-(2-(4-methylpiperazin-1-yl)-2-oxeoethyl)benzo[d]thiazol-2(3H)-one, J. mol. Struc., 980, 230-244(2010).

http://dx.doi.org/10.1016/j.molstruc.2010.07.022 

Krishnakumar, V., Prabavathi, N., Structure and vibrational frequencies of 6,7-dimethoxy-1,4-dihydro-1,3-quinoxalinedione based on density functional theory calculations: The role of electron conjugation and back-donation, Spectrochim. Acta, 77, 238-247 (2010).

http://dx.doi.org/10.1016/j.saa.2010.05.015

Pavia, D. I., Lampman, G. M., Kriz, G. S., Physics, in: J. Vondeling (Ed.), Introduction to Spectroscopy: A Guide for Student of Organic chemistry, third ed., Thomson, Learning, 2001.

Prabavathi, N., Nilufer, A., Krishnakumar, V., FT-IR, FT-Raman and DFT quantum chemical study on the molecular conformation, vibrational and electronic transitions of 1-(m- (trifluoromethyl)phenyl)piperazine, Spectrochim. Acta, 121, 483-493 (2014).

http://dx.doi.org/10.1016/j.saa.2013.10.102

Prabavathi, N., Nilufer, A., Krishnakumar, V., Vibrational spectroscopic (FT-IR and FT-Raman) studies, natural bond orbital analysis and molecular electrostatic potential surface of Isoxanthopterin, Spectrochim. Acta, 114,101-113 (2013).

http://dx.doi.org/10.1016/j.saa.2013.05.013 

Prabavathi, N., Senthil Nayaki, N., Molecular structure, FT-IR, FT-Raman, NMR studies and first order molecular hyperpolarizabilities of 7-methoxy-4-methylcoumarin by DFT Method, Phys. Express 4(12), 1-15 (2014).

Prasad, M.V.S., Kadali Chaitanya, UdayaSri, N., Veeraiah, V., Experimental and theoretical (HOMO, LUMO, NBO analysis and NLO properties) study of 7-hydroxy-4-phenylcoumarin and 5,7-dihydroxy-4-phenylcoumarin J. Mol. Struct. 1047 (2013) 216-228.

http://dx.doi.org/10.1016/j.molstruc.2013.04.066

Sebastian, S., Sundaraganesan, N., Karthikeiyan, B., Srinivasan, V., Quantum mechanical study of the structure and spectroscopic (FT-IR, FT-Raman, 13C, 1H and UV), first order hyperpolarizabilities, NBO and TD-DFT analysis of the 4-methyl-2-cyanobiphenyl, Spectrochim. Acta , 8, 590-600 (2011).

http://dx.doi.org: 10.1016/j.saa.2010.11.028

Sebastian, S., Sylvestre, S., Sundaraganesan, N., Amalanathan, M., Ayyapan, S., Oudayakumar, K., Karthikeyan, B., Vibrational spectra, molecular structure, natural bond orbital, first order hyperpolarizability, TD-DFT and thermodynamic analysis of 4-amino-3- hydroxy-1-naphthalenesulfonic acid by DFT approach, Spectrochim. Acta ,107,167-178(2013). 

http://dx.doi.org/10.1016/j.saa.2013.01.041

Silverstein, M., Clayton Basseler, G., Morill, C., Spectrometric Identification of Organic Compound, Wiley, New York, 1981.

Sylvestre, S., Sebastian, S., Oudayakumar, K., Jayavarthanan, T., Sundaraganesan, N., Experimental (FT-IR, FT-Raman and UV-Vis) spectra and theoretical DFT investigations of 2,3-diaminophenazine, Spectrochim. Acta, 96, 401-412 (2012). 

http://dx.doi.org/10.1016/j.saa.2012.05.047

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