Abstract
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.
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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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
J.J. Gilman: “Mechanochemistry”,Science, Vol. 274, (1996), p. 65.
L.D. Field, S. Sternhell, H.V. Wilton and V. Howard: “Mechanochemistry of somehydrocarbons”,Tetrahedron, Vol. 53, (1997), pp. 4051–4062.
J.F. Fernández-Bertrán: “Mechanochemistry: an overview”,Pure Appl. Chem., Vol. 71, (1999), pp. 581–586.
N. Shan, F. Toda and W. Jones: “Mechanochemistry and co-crystal formation: effect of solvent on reaction kinetics”,Chem. Commun., (2002), pp. 2372–2373.
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.
A.V. Trask, W.D.S. Motherwell and W. Jones: “Solvent-drop grinding: green polymorph control of cocrystallisation”,Chem. Commun., (2004), pp. 890–891.
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.
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.
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.
H. Bredereck and G. Theilig: “Imidazolsynthesen mit Formamid (Formamid-Reaktionen, I. Mitteril)”,Chem. Ber, Vol. 86, (1952), pp. 88–96.
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.
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.
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.
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.
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.
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.
J. Elguero, C. Marzin, A.R. Katritzky and P. Linda: The Tautomerism of Heterocycles, Academic Press, New York, 1976.
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.
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.
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López, C., Claramunt, R.M., García, M.Á. et al. Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy. cent.eur.j.chem. 2, 660–671 (2004). https://doi.org/10.2478/BF02482729
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DOI: https://doi.org/10.2478/BF02482729