Abstract
Solutions of salicylaldehyde benzoyl hydrazone (SBH) in mixed DMSO/H2O solvents have been studied by IR and NMR spectroscopy. Adding water to dilute solutions in DMSO changes the major conformation from the fully extended E isomer denoted B2E to another E isomer, B1E, where the carbonyl is associated with water. A minor Z form, B2Z, is also detected both in DMSO and in the mixed solvent. Near saturation in the mixed solvent, the major species has an imidinol function and the ratio B2Z/B1E increases. Raising the pH also favors the Z configuration. According to quantum mechanical calculations, the B2Z imidinol or monodeprotonated forms are stabilized by several kcal-mol−1 with respect to their B1E and B2E counterparts, whereas the reverse is true for free or hydrated ketones. Free B2E ketone is calculated to be slightly more stable than its B1E counterpart, but the specific association with water reverses the situation. The balance between B1E, B2E, and B2Z forms appears to depend mainly on steric strain release and on hydrogen bond formation involving either both nitrogens, N1 and N2, of the hydrazone or at least one of them, N1 for the E configuration or N2 for the Z one. Calculation indicates that the first deprotonation occurs at the NH site for the B1E and B2E forms, but at the OH phenol site for B2Z.
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Ponka, P.; Borova, J.; Neuwirt, J.; Fuchs, O. FEBS Lett. 1979, 97, 317; Richardson, D. R.; Ponka, P. J. Lab. Clinic. Med. 1998, 131, 306.
Ponka, P.; Borova, J.; Neuwirt, J.; Fuchs, O.; Necas, E. Biochim. Biophys. Acta 1979, 586, 278.
Johnson, D. K.; Pippard, M. J.; Murphy, T.B.; and Rose, N. J. J. Pharmacol. Exp. Ther. 1982, 221, 399.
Avramovici-Grisaru, S.; Sarel, S.; Link, G.; Hershko, C. J. Med. Chem. 1983, 26, 298.
Dimmock, J. R.; Baker, G. B.; Taylor, W. G. Can. J. Pharm. Sci. 1972, 7, 100.
Johnson, D. K.; Murphy, T. B.; and Rose, N. J.; Goodwin, W. H.; Pickart, L. Inorg. Chim. Acta 1982, 67, 159.
Dubois, J. E.; Fakhrayan, H.; Doucet, J. P.; El Hage Chahine, J. M. Inorg. Chem. 1992, 31, 853.
Lyubchova, A.; Cossé-Barbi, A.; Doucet, J. P.; El Hage Chahine, J. M. J. Chim. Phys. 1997, 94, 1195.
Colonna, C.; Cossé-Barbi, A.; Massat, A.; Abdelmoumene, R.; Doucet, J. P. Bull. Soc. Chim. Belg. 1993, 102, 411.
Colonna, C.; Doucet, J. P.; Cossé-Barbi, A. Spectrosc. Lett. 1994, 27, 1153.
Colonna, C.; Doucet, J. P.; Cossé-Barbi, A. Transition Met. Chem. 1995, 20, 338.
Vauthier, E.; Maurel, F.; Couesnon, T.; Cossé-Barbi, A. Spectrosc. Lett. 1999, 32, 505.
Grammaticakis, P. Bull. Soc. Chim. Fr. 1950, p. 690.
Murphy, T. B.; and Rose, N. J.; Schomaker, V.; Aruffo, A. A. Inorg. Chim. Acta 1985, 108, 183.
Lyubchova, A.; Cossé-Barbi, A.; Doucet, J. P.; Robert, F.; Souron, J. P.; Quarton, M. Acta Crystallogr. 1995, C51, 1893.
Aruffo, A. A.; Murphy, T. B.; Johnson, D. K.; Rose, N. J.; Schomaker, V. Inorg. Chim. Acta 1982, 67, L25.
Aruffo, A. A.; Murphy, T. B.; Johnson, D. K.; Rose, N. J.; Schomaker, V. Acta Crystallogr. 1984, C40, 1164.
Ainscough, E. W.; Brodie, A. M.; Ranford, J. D.; Waters, J. M. Inorg. Chim. Acta 1995, 236, 83.
Ainscough, E. W.; Brodie, A. M.; Dobbs, A. J.; Ranford, J.D.; Waters, J. M. Inorg. Chim. Acta 1998, 267, 27.
Banβe, W.; Ludwig, E.; Mickler, W.; Uhlemann, E.; Hahn, E.; Lugger, Th.; Lehmann, A. Z. Anorg. Allgem. Chem. 1995, 621, 1483.
Dutta, S.; Manivannan, V.; Babu, L. G.; Pal, S. Acta Crystallogr. 1995, C51, 813.
Banβe, W.; Ludwig, E.; Schilde, U.; Uhlemann, E.; Weller, F.; Lehmann, A. Z. Anorg. Allgem. Chem. 1995, 621, 1275.
Khudoyarov, A. B.; Sharipov, Kh. T. Uzb. Khim. Zh. 1991, p. 3.
Gulbaev, Ya. I.; Azizov, T. A.; Khudoyarov, A. B.; Sharipov, Kh. T. Uzb. Khim. Zh. 1997, p. 28.
Lyubchova, A.; Jouini, N.; Massat, A.; Doucet, J. P.; Boubekeur, K.; Cossé-Barbi, A. Z. Kristallogr. 2001, 216, 560.
Arai, T.; Moriyama, M.; Tokumaru, K. J. Amer. Chem. Soc. 1994, 116, 3171.
Lewis, F. D.; Yoon, B. A. J. Org. Chem. 1994, 59, 2537.
Mague, J. T.; Vang, S.; Berge, D. G.; Wacholtz, W. F. Acta Crystallogr. 1997, C53, 973.
Pearson, R. G. J. Amer. Chem. Soc. 1963, 85, 3533.
Delsuc, M. A. in Maximum Entropy and Bayesian Methods; Skilling, J., ed.; Kluwer Academic: Dordrecht, 1988; pp. 285–290.
Pons, J. L.; Malliavin, T. E.; Delsuc, M. A. J. Biomol. NMR 1996, 8, 445
Hwang, T. L.; Shaka, A. J. J. Amer. Chem. Soc. 1992, 114, 3157.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. GAUSSIAN 98 Revision A. 6; Gaussian Inc: Pittsburgh, PA, 1998.
Cramer, C. J.; Truhlar, D. G. J. Comp.-Aided Mol. Design 1992, 6, 629.
Cossi, M.; Barone, V.; Cammi, R.; Tomasi, J. Chem. Phys. Lett. 1996, 255, 327.
Pearson, R. G. J. Amer. Chem. Soc. 1986, 108, 6109.
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Cordier, C., Vauthier, E., Adenier, A. et al. Salicylaldehyde Benzoyl Hydrazone: Isomerization Due to Water. A Structural Analysis Using a Combination of NMR, IR, and Theoretical Investigations. Structural Chemistry 15, 295–307 (2004). https://doi.org/10.1023/B:STUC.0000026744.76622.2c
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DOI: https://doi.org/10.1023/B:STUC.0000026744.76622.2c