Experimental Study of Tautomeric Equilibria of 2-Cyanobenzoic Acids in Gas, Solution and Solid Phase
DOI:
https://doi.org/10.6000/1929-5030.2012.01.02.6Keywords:
Cyanobenzoic acids, mass spectrometry, NMR, infrared spectroscopyAbstract
2-cyanobenzoic acids are very important compounds in several sciences, and it is because of this that studying their tautomeric equilibria is of great interest. Ring-chain tautomeric equilibria of 2-, 3- and 4- cyanobenzoic, 3-benzyl-2-cyanobenzoic and 1-cyano-2-naphthoic acids were studied in gas phase by means of mass spectrometry (MS). Furthermore, evidences of ring-chain tautomerism of 2-cyanobenzoic acid were found in solution using 1H and 13C nuclear magnetic resonance and in solid phase by infrared spectroscopy.References
[1] Claramunt RM, Elguero J. Una aproximación a la tautomería de los heterociclos aromáticos. An Quím 2006; 102(4): 30-9.
[2] Raczynska ED, Kosinska W. Tautomeric equilibria in relation to Pi-electron delocalization. Chem Rev 2005; 105: 3561- 612. http://dx.doi.org/10.1021/cr030087h
[3] Jones PR, Saltzman MD, Panici RP. Models for the study of macrocyclic ring-chain tautomerism. J Org Chem 1970; 35: 1200-7. http://dx.doi.org/10.1021/jo00829a085
[4] Allegretti PE, Milazzo CB, Furlong JJP. Mass spectrometry as a tool for the determination of heats of tautomerization of thioamides in the gas phase. Eur J Mass Spectrom 2005; 11: 53-64. http://dx.doi.org/10.1255/ejms.691
[5] Allegretti PE, Schiavoni MM, Guzman Sampay C, Ponzinibbio A, Furlong JJP. Mass spectral study of the occurrence of tautomeric forms of thiohydantoins. Eur J Mass Spectrom 2007; 3: 291-306. http://dx.doi.org/10.1255/ejms.885
[6] Giussi JM, Ponzinibbio A, Cortizo MS, Allegretti PE. 3- Hydroxy-4-methyl-4-pentenonitrile and 4-methyl-3-oxo-4- pentenonitrile: Study of the tautomerics equilibria in gas phase and in solution. Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 2010; 77: 367-73. http://dx.doi.org/10.1016/j.saa.2010.04.003
[7] Saravi Cisneros H, Laurella SL, Ruiz DL, Allegretti PE, Ponzinibbio A, Furlong JJP. Spectrometric Study of the Nitrile-Ketenimine Tautomerism. Int J Spectrosc 2009; Article ID 408345, 18pages. doi:10.1155/2009/408345.
[8] Giussi JM, Gastaca B, Albesa A, Cortizo MS, Allegretti PE. Determination of thermodynamic parameters of tautomerization in gas phase by mass spectrometry and DFT calculations: Keto-enol versus nitrile–ketenimine equilibria. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2011; 78: 868-73. http://dx.doi.org/10.1016/j.saa.2010.12.050
[9] Ruiz DL, Schiavoni MM, Laurella SL, Giussi JM, Furlong JJP, Allegretti PE. The evidence for the occurrence of tautomeric structures for selected aldehydes and thioaldehydes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2011; 78: 1397-402. http://dx.doi.org/10.1016/j.saa.2011.01.017
[10] Saravi Cisneros H, Erben M, Della Vedova CO, Laurella SL, Allegretti PE, Furlong JJP. Determination of Heats of Tautomerization Nitrile-Ketenimine by Mass Spectrometry. Eur J Mass Spectrom 2011; 17(2): 125-43. http://dx.doi.org/10.1255/ejms.1112
[11] Allegretti PE, Schiavoni MM, Di Loreto H, Furlong JJP, Della Vedova CO. Separation of Keto-Enol tautomers in - ketoesters: A Gas Chromatography-Mass Spectrometric Study J Mol Struct 2001; 560: 327-35. http://dx.doi.org/10.1016/S0022-2860(00)00773-0
[12] Barros MT, Geraldes CFGC, Mavcock CD, Silva MI. A proton and 13C NMR study of keto-enol tautomerism of some - ketoamides. J Mol Struct 1986; 142: 435-8. http://dx.doi.org/10.1016/0022-2860(86)85150-X
[13] Ruiz DL, Albesa AG, Ponzinibbio A, Allegretti PE, Schiavoni MM. Solvent effects on tautomerics equilibria in - ketonitriles. NMR and Theoretical Studies. J Phys Org Chem 2010; 23(10): 985-94. http://dx.doi.org/10.1002/poc.1764
[14] Bunting JW, Kanter JP. Acidity and tautomerism of -keto esters and amides in aqueous solution. J Am Chem Soc 1993; 115: 11705-15. http://dx.doi.org/10.1021/ja00078a008
[15] Yamasaki K, Kajimoto O. Solvent effect in supercritical fluids: keto-enol equilibria of acetylacetone and ethyl acetoacetate. Chem Phys Lett 1990; 172: 271-4. http://dx.doi.org/10.1016/0009-2614(90)85401-W
[16] Furniss BS, Hannaford AJ, Smith PWG, Tatchell AR. VOGEL’s textbook of practical organic chemistry, fifth edition, London, Longman 1999.
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Published
2012-12-31
How to Cite
Iglesias, D. A., Ruiz, D. L., & Allegretti, P. E. (2012). Experimental Study of Tautomeric Equilibria of 2-Cyanobenzoic Acids in Gas, Solution and Solid Phase. Journal of Applied Solution Chemistry and Modeling, 1(2), 113–120. https://doi.org/10.6000/1929-5030.2012.01.02.6
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