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.
Downloads
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
Issue
Section
General Articles
License
Policy for Journals/Articles with Open Access
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work
Policy for Journals / Manuscript with Paid Access
Authors who publish with this journal agree to the following terms:
- Publisher retain copyright .
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work .
