Carbonyl stretching vibrations of 5-halogen-2-thiophenecarboxaldehydes: KBM, AN, SWAIN and LSER parameters

Abstract

Halogen and solvent influence on the conformational stability and carbonyl stretching vibration of 5-Halogeno-2-thiophenecarboxaldehydes (C5H3XOS; X=F, Cl or Br) were investigated by the density functional theory using the B3LYP functional, 6-311+G(3df,p) basis set and polarizable continuum model. Calculations were performed by the cis and trans forms of the compounds in eighteen different solvents. The carbonyl stretching frequencies were correlated with some solvent parameters such as the Kirkwood-Bauer-Magat equation, the solvent acceptor number, Swain parameters and the linear solvation energy relationships. The findings of this research will be useful for thiophenecarboxaldehydes.

Keywords

• 5-Halogeno-2-thiophenecarboxaldehyde
• DFT
• Solvent effect

5-halojen-2-tiyofenkarboksaldehitlerin karbonil gerilme titreşimleri: KBM, AN, SWAIN ve LSER parametreleri

Öz

5-halojen-2-tiyofenkarboksaldehitlerin (C5H3XOS; X=F, Cl veya Br) yapısal denge ve karbonil gerilme titreşimleri üzerindeki çözücü ve halojen etkileri yoğunluk fonksiyoneli teorisi ile B3LYP fonksiyoneli, 6-311+G(3df,p) baz seti ve kutuplanabilir süreklilik modeli kullanılarak incelendi. Hesaplamalar on sekiz farklı çözücü içinde moleküllerin cis ve trans konformasyonları ele alınarak yürütüldü. Çözücü içindeki karbonil gerilme titreşim frekansları Kirkwood-Bauer-Magat denklemi, çözücü akseptör sayısı, Swain parametreleri ve lineer çözünme enerji ilişkisi gibi çözücü skalaları ile incelendi. Bu çalışmanın sonuçları tiyofen-karboksaldehit türevleri için faydalı olacaktır.

Anahtar Kelimeler

• 5-Halojen-2-tiyofenkarboksaldehit
• YFT
• Çözücü etkisi

Kaynakça

1. Szkurlat A, Palys B, Mieczkowski J, Skompska M. “Electrosynthesis and spectroelectrochemical characterization of poly(3,4-dimethoxy-thiophene), Poly(3,4-dipropyloxythiophene) and poly(3,4-dioctyloxythiophene) films”. Electrochimica Acta, 48(24), 3665-3676, 2003.
2. Kumar PR, Raju S, Goud PS, Sailaja M, Sarma RM, Reddy GO, Kumar MP, Reddy VVRM-K, Suresha T, Hegdeb P. “Synthesis and Biological Evaluation of Thiophene [3,2-b] pyrrole derivatives as potential anti-inflammatory agents”. Bioorganic & Medicinal Chemistry, 12(5), 1221-1230, 2004.
3. Giordanetto F, Karlsson O, Lindberg J, Larsson LO, Linusson A, Evertsson E, Morgan DGA, Inghardt T. “Discovery of Cyclopentane- and cyclohexane-trans-1,3-diamines as potent melanin-concentrating hormone receptor 1 antagonists”. Bioorganic & Medicinal Chemistry Letters, 17(15), 4232-4241, 2007.
4. Brault L, Migianu E, Neguesque A, Battaglia E, Bagrel D, Kirsch G. “New thiophene analogues of kenpaullone: synthesis and biological evaluation in breast cancer cells”. European Journal of Medicinal Chemistry, 40(8), 757-763, 2005.
5. Kao J, Radom L. “Conformations, stabilities, and charge distributions in 2- and 3-monosubstituted thiophenes. An ab initio molecular orbital study”. Journal of the American Chemical Society, 101(2), 311-318, 1979.
6. Lunazzi L, Placucci G, Chatgilialoglu C, Macciantelli D. “Conformational studies by dynamic nuclear magnetic resonance. part 26. interconversion barriers between syn- and anti-conformers of isomeric thiophenecarbaldehydes”. Journal of the Chemical Society, Perkin Transactions, 4, 819-822, 1984.
7. Braathen GO, Kveseth K, Nielsen CJ, Hagen K. “‘Molecular structure and conformational equilibrium of gaseous thiophene-2-aldehyde as studied by electron diffraction and microwave, infrared, raman and matrix isolation spectroscopy”. Journal of Molecular Structure, 145(1-2), 45-68, 1986.
8. Fleming GD, Koch R, Vallete MMC. “Theoretical study of the syn and anti thiophene-2-aldehyde conformers using density functional theory and normal coordinate analysis”. Spectrochimica Acta A: Molecular and Biomolecular Spectroscopy, 65(3-4), 935-945, 2006.

9. Tursun M, Parlak C. “Conformation Stability, Halogen and Solvent Effects on C=O Stretching of 4-chloro-3-halogenobenzaldehydes”. Spectrochimica Acta A: Molecular and Biomolecular Spectroscopy, 141, 58-63, 2015.
10. Levinson NM, Fried SD, Boxer SG. “Solvent-Induced infrared frequency shifts in aromatic nitriles are quantitatively described by the vibrational stark effect”. The Journal of Physical Chemistry B, 116(35), 10470-10476, 2012.
11. Chen Y, Morisawa Y, Futami Y, Czarnecki MA, Wang HS, Ozaki Y. “Combined IR/NIR and density functional theory calculations analysis of the solvent effects on frequencies and intensities of the fundamental and overtones of the C=O stretching vibrations of acetone and 2-hexanone”. The Journal of Physical Chemistry A, 118(14), 2576-2583, 2014.
12. Jovic B, Nikolic A, Petrovic S. “FTIR spectroscopic study of hydrogen bonding and solvent induced frequency shifts of N-tert-butylacetamide”. Journal of Molecular Structure, 1044, 140-143, 2013.
13. Ji X, Li Y, Zheng J, Liu Q. “Solvent effects of ethyl methacrylate characterized by FTIR”. Materials Chemistry and Physics, 130(3), 1151-1155, 2011.
14. Vdovenko SI, Gerus II, Kukhar VP. “Solvent effects on the infrared spectra of β-alkoxyvinyl methyl ketones: I. carbonyl and vinyl stretching vibrations”. Spectrochimica Acta A: Molecular and Biomolecular Spectroscopy, 71(3), 779-785, 2008.
15. Stolov AA, Herrebout WA, Van der Veken BJ. “Solvent effect on vibrational frequencies: cryosolution experiments and density functional calculations”. Journal of Molecular Structure, 480-481, 499-503, 1999.
16. West W, Edwards RT. “The infrared absorption spectrum of hydrogen chloride in solution”. The Journal of Chemical Physics, 5, 14-22, 1937.
17. Bauer E, Magat M. “Deformation of molecules in condensed phases and the hydrogen bond”. Journal de Physique et le Radium, 9(8), 319-330, 1938.
18. Gutmann V, Resch G. The Donor-Acceptor Interactions, New York, USA, Plenum Press, 1978.
19. Swain CG, Swain MS, Powell AL, Alunni S. “Solvent effects on chemical reactivity. Eevaluation of anion- and cation-solvation components”. Journal of the American Chemical Society, 105(3), 502-513, 1983.
20. Kamlet MJ, Abboud JLM, Abraham MH, Taft RW. “Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, .Pi.*, .alpha., and .beta., and Some Methods for simplifying the generalized solvatochromic equation”. The Journal of Organic Chemistry, 48(17), 2877-2887, 1983.
21. Frisch MJ, Trucks GW, Schlegel HB, et al. Gaussian 09, Revision A.1, Gaussian Inc., Wallingford, CT, 2009.
22. Parlak C. “Theoretical and experimental vibrational spectroscopic study of 4-(1-Pyrrolidinyl) piperidine”. Journal of Molecular Structure, 966(1-3), 1-7, 2010.
23. Sowula M, Misiaszek T, Bartkowiak W. “Solvent effect on the vibrational spectrum of michler’s ketone. experimental and theoretical investigations”. Spectrochimica Acta A: Molecular and Biomolecular Spectroscopy, 131, 678-685, 2014.
24. Chen Y, Zhang H, Liu Q. “FT-IR spectroscopy combined with DFT calculation to explore solvent effects of vinyl acetate”. Spectrochimica Acta A: Molecular and Biomolecular Spectroscopy, 126, 122-128, 2014.
25. Parlak C, Kumar CSC, Fun HK, Keşan G, Rhyman L, Ramasami P, Chandraju S, Quah CK. “4-Chloro-3-fluorobenzaldehyde: Experimental (XRD, FT-IR and raman) and DFT studies”. Journal of Fluorine Chemistry, 163, 7-15, 2014.