Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy

• Authors: Concepción López , Rosa Claramunt , M. García , José Elguero
• Languages of publication: EN

Abstracts

EN

Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by13C and 15N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists.

Keywords

EN

Pyrazoles; imidazoles; tautomerism; solid-state NMR; DSC

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2004
• Volume: 2
• Issue: 4
• Pages: 660-671

Dates

published

1 - 12 - 2004

online

1 - 12 - 2004

Contributors

author

Concepción López

• Departmento de Química Orgánica y Biología, Facultad de Ciencias, UNED, Senda del Rey 9, E-28040, Madrid, Spain

author

Rosa Claramunt

• Departmento de Química Orgánica y Biología, Facultad de Ciencias, UNED, Senda del Rey 9, E-28040, Madrid, Spain

author

M. García

• Departmento de Química Orgánica y Biología, Facultad de Ciencias, UNED, Senda del Rey 9, E-28040, Madrid, Spain

author

José Elguero

• Instituto de Química Médica, CSIC, Juan de la Cierva 3, E-28006, Madrid, Spain

References

• [1] A. Baldy, J. Elguero, R. Faure, M. Pierrot and E.-J. Vincent: “Dynamic Intermolecular Tautomerism of 3,5-Dimethylpyrazole in the Solid State by13C CP/MAS NMR Spectroscopy and X-Ray Crystallography”,J. Am. Chem. Soc., Vol. 107, (1985), pp. 5290–5291. http://dx.doi.org/10.1021/ja00304a053[Crossref]
• [2] J.A.S. Smith, B. Wehrle, F. Aguilar-Parrilla, H.-H. Limbach, C. Foces, F.H. Cano, J. Elguero, A. Baldy, M. Pierrot, M.M.T. Khurshid and J.B. Larcombe: “Intermolecular Triple Proton and Deuteron Transfert in Crystalline 3,5-Dimethylpyrazole Studied by NMR, NQR, and X-Ray Methods”,J. Am. Chem. Soc., Vol. 111, (1989), pp. 7304–7312. http://dx.doi.org/10.1021/ja00201a004[Crossref]
• [3] F. Aguilar-Parrilla, G. Scherer, H.-H. Limbach, C. Foces-Foces, F.H. Cano and J. Elguero: “Observation of a Séries of Degenerate Cyclic Double, Triple, and Quadrupole Proton Transfers in Solid Pyrazoles”,J. Am. Chem. Soc., Vol. 114, (1992), pp. 9657–9659. http://dx.doi.org/10.1021/ja00050a055[Crossref]
• [4] F. Toda, K. Tanaka, C. Foces-Foces, A.L. Llamas-Saiz, H.-H. Limbach, F. Aguilar-Parrilla, R.M. Claramunt, C. López and J. Elguero: “Intermolecular Proton Transfer in Host-Guest Crystals: The Case of Pyrazole Included in 1,1-Di(2,4-dimethylphenyl)but-2-yn-1-ol, An X-Ray and Solid-Sate13C/15N NMR Study”,J. Chem. Soc., Chem. Comm., (1993), pp. 1139–1142.
• [5] J. Elguero, F.H. Cano, C. Foces-Foces, A.L. Llamas-Saiz, H.-H. Limbach, F. Aguilar-Parrilla, R.M. Claramunt and C. López: “Proton Transfer in Solid Heterocycles: An X-Ray and CPMAS NMR Study”,J. Heterocycl. Chem., Vol. 31, (1994), pp. 695–700. http://dx.doi.org/10.1002/jhet.5570310310[Crossref]
• [6] F. Aguilar-Parrilla, R.M. Claramunt, C. López, D. Sanz, H.-H. Limbach and J. Elguero: “High-Resolution Solid-State13C and 15N NMR Spectroscopy of Pyrazole and 3,5-Dimethylpyrazole Adsorbed on Alumina and Silica”,J. Phys. Chem., Vol. 98, (1994), pp. 8752–8760. http://dx.doi.org/10.1021/j100086a027[Crossref]
• [7] J. Elguero, H.H. Limbach, F. Aguilar-Parrilla, R.M. Claramunt and C. López: “Resonancia magnética nuclear de alta resolución en estado sólido: un auxiliar de la cristalografía”,Nuevas Tendencias Cristalografía, CSIC, (1995), pp. 287–309.
• [8] F. Aguilar-Parrilla, H.-H. Limbach, C. Foces-Foces, F.H. Cano, N. Jagerovic and J. Elguero: “Structure and Dynamics of 3,5-Di- Tert-Butylpyrazole Probed by Combined X-Ray Crtystallography and 15N Solid State NMR”,J. Org. Chem., Vol. 60, (1995), pp. 1965–1970. http://dx.doi.org/10.1021/jo00112a015[Crossref]
• [9] C. Foces-Foces, L. Infantes, F. Aguilar-Parrilla, N.S. Golubev, H.-H. Limbach and J. Elguero. “Mixed Crystals of Pyrazoles and Benzoic Acids. Part I. The Molecular Structure of 3,5-Dimethylpyrazole-2,4,6-Trimethylbenzoic Acid Co-Crystals”,J. Chem. Soc., Perkin Trans. 2, (1996), pp. 349–353. [Crossref]
• [10] F. Aguilar-Parrilla, O. Klein, J. Elguero and H.-H. Limbach: “A Dynamic 15N NMR Study of Kinetic Hydrogen/Deuterium Isotope and Tunnel Effects on the Triple Proton Transfer in Crystalline 3,5-Dimethylpyrazole”,Ber. Bunsenges. Phys. Chem., Vol. 101, (1997), pp. 889–901.
• [11] R.M. Claramunt, M.D. Santa María, I. Forfar, F. Aguilar-Parrilla, M. Minguet-Bonvehí, O. Klein, H.-H. Limbach, C. Foces-Foces, A.L. Llamas-Saiz and J. Elguero: “Molecular Structure and Dynamics ofC-1-Adamantyl SubstitutedN-Unsubstituted Pyrazoles Studied by Solid State NMR Spectroscopy and X-Ray Crystallography”,J. Chem. Soc., Perkin Trans. 2, (1997), pp. 1867–1875. [Crossref]
• [12] O. Klein, M. Minguet-Bonvehí, F. Aguilar-Parrilla. N. Jagerovic, J. Elguero and H.-H. Limbach: “Hydrogen Bond Compression during Triple Proton Transfer in Crystalline Pyrazoles. A Dynamic 15N NMR Study”,Israel J. Chem., Vol. 39, (1999), pp. 291–299.
• [13] C. Foces-Foces, A. Echevarría, N. Jagerovic, I. Alkorta, J. Elguero, U. Langer, O. Klein, M. Minguet-Bonvehí and H.-H. Limbach: “A Solid-State NMR, X-ray Diffraction andab initio Computational Study of Hydrogen-Bond Structure and Dynamics of Pyrazole-4-Carboxylic Acid Chains”,J. Am. Chem. Soc., Vol. 123, (2001), pp. 7896–7906. http://dx.doi.org/10.1021/ja002688l[Crossref]
• [14] H.-H. Limbach, O. Klein, J.M. López del Amo and J. Elguero: “Multiple Kinetic Hydrogen/Deuterium Isotope effects in Quadruple Proton Transfer Reactions”,Z. Phys. Chem., Vol. 218, (2004), pp. 19–49.
• [15] D.R. Trivedi, A. Ballabh and P. Dastisar: “Supramolecular assemblies in salts and co-cyrstals of imidazoles with dicarboxylic acids”,Cryst. Eng. Comm., Vol. 5, (2003), pp. 358–367. [Crossref]
• [16] I. Boldog, E.B. Rusanov, J. Sieler and K.V. Domasevich: “Cooperative association of pyrazoles and phenols: a versatile binary system”,New J. Chem., Vol. 28, (2004), in press.
• [17] J.J. Gilman: “Mechanochemistry”,Science, Vol. 274, (1996), p. 65. http://dx.doi.org/10.1126/science.274.5284.65[Crossref]
• [18] L.D. Field, S. Sternhell, H.V. Wilton and V. Howard: “Mechanochemistry of somehydrocarbons”,Tetrahedron, Vol. 53, (1997), pp. 4051–4062. http://dx.doi.org/10.1016/S0040-4020(97)00017-3[Crossref]
• [19] J.F. Fernández-Bertrán: “Mechanochemistry: an overview”,Pure Appl. Chem., Vol. 71, (1999), pp. 581–586.
• [20] N. Shan, F. Toda and W. Jones: “Mechanochemistry and co-crystal formation: effect of solvent on reaction kinetics”,Chem. Commun., (2002), pp. 2372–2373. [Crossref]
• [21] Y. Murata, A. Han and K. Komatsu: “Mechanochemical synthesis of a novel C 60 dimer connected by a germanium bridge and a single bond”,Tetrahedron Letters, Vol. 44, (2003), pp. 8199–8201. http://dx.doi.org/10.1016/j.tetlet.2003.09.077
• [22] A.V. Trask, W.D.S. Motherwell and W. Jones: “Solvent-drop grinding: green polymorph control of cocrystallisation”,Chem. Commun., (2004), pp. 890–891. [Crossref]
• [23] A. Cammers and S. Parkin: “Solid state hydrogen bonding in imidazole derivatives: a persistent tape motif”,Cryst. Eng. Comm., Vol. 6, (2004), pp. 168–172. [Crossref]
• [24] E. Escande, J. Lapasset, R. Faure, E.J. Vincent and J. Elguero: “Les benzazoles (indazole, benzimidazole, benzotriazole): structure moléculaire et propriétésfondamentales”,Tetrahedron, Vol. 30, (1974), pp. 2903–2909. http://dx.doi.org/10.1016/S0040-4020(01)97464-2[Crossref]
• [25] R.M. Claramunt, M.D. Santa-María, L. Infantes, F.H. Cano and J. Elguero: “The annular tautomerism of 4(5)-phenylimidazole”,J. Chem. Soc., Perkin Trans. 2, (2002), pp. 564–568. [Crossref]
• [26] H. Bredereck and G. Theilig: “Imidazolsynthesen mit Formamid (Formamid-Reaktionen, I. Mitteril)”,Chem. Ber, Vol. 86, (1952), pp. 88–96.
• [27] R.M. Claramunt, C. López, M.Á. García, G.S. Denisov, I. Alkorta and J. Elguero: “Protonation and phase effects on the NMR chemical shifts of imidazoles and pyrazoles: experimental results and GIAO calculations”,New J. Chem., Vol. 27, (2003), pp. 734–742. http://dx.doi.org/10.1039/b210251j[Crossref]
• [28] S.J. Opella and M.H. Frey: “Selection of nonprotonated carbon resonances in solid-state nuclear magnetic resonance”,J. Am. Chem. Soc., Vol. 101, (1979), pp. 5855–5856.
• [29] J. Alcázar, A. de la Hoz and M. Begtrup: “Carbon-13 NMR spectra of imidazole 1-oxides. Comparison with parent imidazoles”,Magn. Reson. Chem., Vol. 36, (1998), pp. 296–299. http://dx.doi.org/10.1002/(SICI)1097-458X(199804)36:4<296::AID-OMR244>3.0.CO;2-D[Crossref]
• [30] M. Begtrup, J. Elguero, R. Faure, P. Camps, C. Estopa, D. Ilavsky, A. Fruchier, C. Marzin and J. de Mendoza: “Effect ofN-substitutents of the 13C NMR parameters of azoles”,Magn. Reson. Chem., Vol. 26, (1988), pp. 134–151. http://dx.doi.org/10.1002/mrc.1260260210[Crossref]
• [31] M. Begtrup, G. Boyer, P. Cabildo, C. Cativiela, R.M. Claramunt, J. Elguero, J.I. Garcia, C. Toiron and P. Vedsø: “ 13C NMR of pyrazoles”,Magn. Reson. Chem., Vol. 31, (1993), pp. 107–168. http://dx.doi.org/10.1002/mrc.1260310202[Crossref]
• [32] R.M. Claramunt, D. Sanz, C. López, J.A. Jiménez, M.L. Jimeno, J. Elguero and A. Fruchier: “Substituent effects on the 15N NMR parameters of azoles”,Magn. Reson. Chem., Vol. 35, (1997), pp. 35–75. http://dx.doi.org/10.1002/(SICI)1097-458X(199701)35:1<35::AID-OMR25>3.0.CO;2-K[Crossref]
• [33] J. Elguero, C. Marzin, A.R. Katritzky and P. Linda: The Tautomerism of Heterocycles, Academic Press, New York, 1976.
• [34] V.I. Minkin, A.D. Garnowskii, J. Elguero, A.R. Katritzky and O.V. Denisko: “The Tautomerism of Heterocycles: Five-Membered Rings with Two or More Heteroatoms”,Adv. Heterocycl. Chem., Vol. 76, (2000), pp. 157–323. http://dx.doi.org/10.1016/S0065-2725(00)76005-3[Crossref]
• [35] R.M. Claramunt, M.D. Santa-María, L. Infantes, F.H. Cano and J. Elguero: “The annular tautomerism of 4(5)-phenylimidazole”,J. Chem. Soc., Perkin Trans. 2, (2002), pp. 564–568. [Crossref]

Identifiers

DOI

10.2478/BF02482729