Tautomeria prototropowa i struktura siarkowych analogów uracyli

• Autorzy: Nowakowska Zdzisława , Wyrzykiewicz Elżbieta

Warianty tytułu

EN

The protometric tautomerism and structure of thio-substituted uracils

• Języki publikacji: PL

Abstrakty

EN

The essential biological importance of uracil and its thio-derivatives, as well as the relatively small size of the parent uracil molecule, have motivated a number of experimental and theoretical studies of this species. There are many examples of biological processes in which the knowledge of the relative stability of different tautomers of one molecule can be very helpful in understanding the molecular mechanism involved. Tautomerism of pyrimidine bases has been studied extensively in the past decades. Both theoretical and experimental efforts have been directed toward the prediction of the molecular structure and properties of possible tautomers. 2-Thiouracil and 4-thiouracil can exist in six tautomeric forms with completed cyclic conjugation (aromatic tautomeres). Non-ring conjugated tautomers also exist, but are likely to be of little importance. 2-Thiouracil and 4-thiouracil can from four mono O-, S- or N-methyl derivatives, each of which can exist in three tautometric forms. It has been realized that the relative population of these forms strongly depends on the environment. In particular, the form dominating in the gas phase, or in the nonpolar solvents, may completely disappear in the crystalline state, or in the polar solvents and may be replaced by another tautmetric from. Theoretical calculations based on the quantum mechanical principles may certainly help to resolve the question of the relative stability of various tautometric froms of thiouracils and to predict the relative gas-phase abundances of those forms. Because of the considerable size of thiouracils by quantum mechanical standard, only semiempirical quasiab initio methods have been applied so far. Crystallographic studies of nucleosides and nucleobases and their derivatives are informative [8, 9] and can be used as a basis for the theoretical evaluation of their electronic structures by a quantum-mechanical approach [10, 11].

Słowa kluczowe

PL

tautomeria prototropowa; tiouracyle

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Wiadomości Chemiczne
• Rocznik: 1999
• Tom: [Z] 53, 5-6
• Strony: 415--424
• Opis fizyczny: Bibliogr. 42 poz., schem., tab.

Twórcy

autor

Nowakowska Zdzisława

• Zakład Spektrometrii Masowej Związków Organicznych, Wydział Chemii, Uniwersytet im. A. Mickiewicza, ul. Grunwaldzka 6, 60-780 Poznań

autor

Wyrzykiewicz Elżbieta

• Zakład Spektrometrii Masowej Związków Organicznych, Wydział Chemii, Uniwersytet im. A. Mickiewicza, ul. Grunwaldzka 6, 60-780 Poznań

Bibliografia

• [1] J. S. Kwiatkowski, T. J. Zieliński, R. Rein, Adv. Quantum Chem., 1986, 18, 85.
• [2] J. S. Kwiatkowski, B. Pullman, Tautomerism and Electronic Structure of Biological Pyri- midines, w: Advances in Heterocyclic Chemistry, A. R. Katritzky, A. J. Boulton Eds, Academic Press, New York 1975, vol. 18, p. 312.
• [3] M. Szczęśniak, M. Szczepaniak, J. S. Kwiatkowski, K. Ku Bulat, W. B. Person, JACS, 1988, 110, 8319.
• [4] J. Elguero, C. Marzin, A. R. Katritzky, P. Linda, The Tautomerism of Heterocycles, w: A. R. Katritzky, A. J. Boulton Eds-, Suppl. 1, Academic Press, New York 1976.
• [5] A. R. Katritzky, M. Szafran, J. Stevens, J. Chem. Soc. Perkin Trans. II, 1989, 1507.
• [6] A. R. Katritzky, G. Baykut, S. Rach wal, M. Szafran, K. C. Caster, J. Eyler, J. Chem. Soc. Perkin Trans. II, 1989, 1499.
• [7] A. Leś, L. Adamowicz, JACS, 1990, 112, 1504.
• [8] D. Voet, A. Rich, Progr. Nucleic Acid Res. Mol. Biol., 1970, 10, 183.
• [9] W. Saenger, D. Suck, Eur. J. Bioch., 1973, 32, 473.
• [10] A. Pullman, B. Pullman, Nature, Lond., 1963, 199, 467.
• [11] J. Leszczyński, Int. J. Quantum Chem.: Quantum Biology Symp., 1991, 18, 9.
• [12] M. Geller, A. Pohorille, A. Jaworski, Biochim. Biophys. Acta, 1973, 331, 1.
• [13] A Buda, J. Mol. Struct. (Theochem), 1987, 149, 185.
• [14] A. Leś, I. Ortega-Blake, Int. J. Quantum Chem., 1986, XXX, 225.
• [15] J. Leszczyński, K. Lammertsma, J. Phys. Chem., 1991, 95, 3128.
• [16] H. Rostkowska, K. Szczepaniak, M. J. Nowak, J. Leszczyński, K. Ku Bulat, W. B. Person, JACS, 1990, 112, 2147.
• [17] A. Leś, L. Adamowicz, J. Phys. Chem., 1990, 94, 7021.
• [18] W. C. Schneider, I. F. Halverstadt, JACS, 1967, 89, 1249.
• [19] W. C. Schneider, I. F. Halverstadt, ibid., 1948, 70, 2626.
• [20] H. Berthod, A. Pullman, C. R. Acad. Sci., 1966, 262C, 76.
• [21] J. Pitha, S. Vasickava, Collect. Czech. Chem. Commun., 1965, 30, 1792.
• [22] H. Mautner, G. Bergson, Acta Chem. Scand., 1963, 17, 1694.
• [23] A Pullman, B. Pullman, Compt. Rend., 1958, 246, 611.
• [24] J. S. Kwiatkowski, B. Lesyng, Int. J. Quantum Chem.: Quantum Biology Symposium, 1979, 6, 391. '
• [25] S. Aruna, G. Shanmugam, Indian J. Chem., 1986, 25A, 256.
• [26] K. Singh, D. K. Rai, R. Rai, Asian J. Phys., 1994, 3(3), 153.
• [27] G. H.-Y. Lin, M. Sundaralingam, S. K. Arora, JACS, 1971, 93, 1235.
• [28] M. Sundaralingam, The Purines — Theory and Experiment, E. D. Bergman and B. Pull-man Eds., p. 73, Israel Acad. Sei. Humanities, Jerusalem, Academic Press, New York 1972.
• [29] G.H.-Y. Lin, M. Sundaralingam, Acta Crystallogr., 1971, Sect. B. 27, 961.
• [30] W. Saenger, D. Suck, J. Mol. Biol., 1971, 60, 87.
• [31] W. Saenger, K. H. Scheit, ibid., 1970, 50, 153.
• [32] W. Saenger, JACS, 1972, 94, 621.
• [33] W. Saenger, D. Suck, Acta Crystallogr., 1971, Sect. B. 27, 2105.
• [34] W. Saenger, D. Suck, K. H. Scheit, FEBS Lett., 1969, 5, 262.
• [35] G. S. Parry, F. Strachan, Acta Crystallogr., 1971, 13, 1035.
• [36] N. Okabe, T. Fuji war a, Y. Yam a gat a, K. Tomita, Bull. Chem. Soc. Jpn., 1983,56,1543.
• [37] D. Tsernoglu, Ph. D. Thesis, Yale Univ., New Haven 1966.
• [38] E. Shefter, H. G. Mautner, JACS, 1967, 89, 1249.
• [39] W. Saenger, D. Suck, Acta Crystallogr., 1971, Sect. B. 27, 1178.
• [40] P. K. Tripathi, M. M. Husain, K. Singh, Asian J. Phys., 1994, 3(2), 89.
• [41] S. W. Hawkinson, Acta Crystallogr., 1977, Sect. B. 33, 80.
• [42] B. Lesyng, W. Saenger, Z. Naturforsch., 1981, 36C, 956.