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Tautomerism of aza cycles: II. Synthesis and structure of 5-substituted 3-(2-hydroxyethylsulfanyl)-1H-1,2,4-triazoles and their salts. Preference of the 1H,4H-1,2,4-triazolium tautomers

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Abstract

New complexing agents, potentially tautomeric 3-(2-hydroxyethylsulfanyl)-1H-1,2,4-triazole, its 5-methyl-and 5-phenyl-substituted analogs, and some their salts, were synthesized, and their structure was discussed on the basis of the 1H and 13C NMR, IR, and mass spectra, X-ray diffraction data, and published data. In keeping with the rule formulated previously for N-unsubstituted 1,2,4-triazoles having dissimilar substituents, the synthesized compounds were found to exist as 3-(2-hydroxyethylsulfanyl)-5-R-1H-1,2,4-triazole tautomers (3-RA-5-RD-1H-1,2,4-triazoly). They are protonated at the nitrogen atom in position 4 of the triazole ring. The 1H and 13C NMR spectra of these compounds in trifluoroacetic acid suggest the presence of two forms due to equilibrium between the neutral and protonated species. Analysis of the crystallographic data for the triazolium salts and published data showed preference of the 1H,4H-1,2,4-triazolium tautomer.

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References

  1. Buzykin, B.I., Mironova, E.V., Nabiullin, V.N., Gubaidullin, A.T., and Litvinov, I.A., Russ. J. Gen. Chem., 2006, vol. 76, no. 9, p. 1534.

    Article  CAS  Google Scholar 

  2. Kaplaushenko, A.G., Kinish, A.G., and Panasenko, E.G., Med. Khim., 2005, vol. 7, no. 2, p. 21.

    CAS  Google Scholar 

  3. Trzhtsinskaya, B.V., Aleksandrova, A.E., and Apakina, E.V., Khim.-Farm. Zh., 1991, vol. 25, no. 3, p. 25.

    CAS  Google Scholar 

  4. Mir, I. and Siddigui, M.T., Tetrahedron, 1970, vol. 26, no. 22, p. 5235.

    Article  CAS  Google Scholar 

  5. Ersan, S., Nacak, S., and Berkem, R., Farmaco, 1998, vol. 53, no. 12, p. 773.

    Article  CAS  Google Scholar 

  6. Amir, M. and Kumar, S., Pharmazie, 2005, vol. 60, no. 3, p. 175; Ref. Zh., Khim., 2005, no. 17 Zh 281.

    CAS  Google Scholar 

  7. Szilagyi, G., Somorai, T., Bozo, E., Lango, J., Nagy, G., Reiter, J., Janaky, J., and Andrasy, F., Eur. J. Med. Chem., 1990, vol. 25, no. 2, p. 95.

    Article  CAS  Google Scholar 

  8. Wujec, M., Pitucha, M., Dobosz, M., Kosikowkcu, U., and Malm, A., Acta Pharm. (Croatica), 2004, vol. 54, no. 3, p. 251; Ref. Zh., Khim., 2005, no. 5 Zh 291.

    CAS  Google Scholar 

  9. El-Barbary, A.A. and Abou-El-Ezz, A.Z., Phosphorus, Sulfur Silicon, 2004, vol. 179, no. 8, p. 1497.

    Article  CAS  Google Scholar 

  10. Turan-Zitouni, G., Kaplancikli, Z.A., Yildiz, M.T., Chevallet, P., and Kaya, D., Eur. J. Med. Chem., 2005, vol. 40, no. 6, p. 607.

    Article  CAS  Google Scholar 

  11. US Patent no. 6 600 057, 2003; Ref. Zh., Khim., 2005, no. 4O88.

  12. Martin, I.J., Lewis, R.J., Bonnert, R.V., Cfge, P., and Moody, G.C., Drug Metab. Dispos., 2003. vol. 31, no. 6, p. 694.

    Article  CAS  Google Scholar 

  13. US Patent no. 6 919 342, 2005; Ref. Zh., Khim., 2006, no. 9 O 107.

  14. Shaker, R.M., Mahmoud, A.F., and Abdal-Lafit, F.F., Phosphorus, Sulfur Silicon, 2005, vol. 180, no. 2, p. 397.

    Article  CAS  Google Scholar 

  15. Chu, C.H., Zhang, Y., Zhang, Z.Y., Li, Z.-C., and Liao, R.-A., Indian J. Chem., Sect. B, 2000, vol. 39, no. 10, p. 791.

    Google Scholar 

  16. Aldoshin, S.M., Sanina, N.A., Rakova, O.A., Shilov, G.V., Kulikov, A.V., Shul’ga, Yu.M., and Ovanesyan, N.S., Izv. Ross. Akad. Nauk, Ser. Khim., 2003, no. 8, p. 1614.

  17. Oprean, L., David, L., Zaharia, V., Conisa, A., and Oprean, R., Stud. Univ. Babes-Bolyai, Chem., 2002, vol. 47, nos. 1–2, p. 179; Ref. Zh., Khim., 2004, no. 9 V 85.

    CAS  Google Scholar 

  18. Song, C.E., Kim, J.-S., Choi, J.H., and Jin, B.W., Heterocycles, 1991, vol. 51, no. 1, p. 161.

    Google Scholar 

  19. Polya, J.B., Comprehensive Heterocyclic Chemistry I, Katritzky, A.R. and Rees, Ch.W., Eds., Oxford: Pergamon, 1984, vol. 5, part 4A, p. 733.

    Google Scholar 

  20. Garratt, P.J., Comprehensive Heterocyclic Chemistry II, Katritzky, A.R., Rees, Ch.W., and Scriven, E.F.V., Eds., Oxford: Pergamon, 1996, vol. 4, p. 127.

    Google Scholar 

  21. Buzykin, B.I., Nabiullin, V.N., Mironova, E.V., Gubaidullin, A.T., and Litvinov, I.A., Abstracts of Papers, Mezhdunarodnaya konferentsiya po khimii geterotsiklicheskikh soedinenii, posvyashchennaya 90-letiyu so dnya rozhdeniya A.N. Kosta (Int. Conf. on the Chemistry of Heterocyclic Compounds, Dedicated to 90th Anniversary of A.N. Kost), Moscow, 2005, Ross. Fond Fundam. Issled., IIKhR, p. 132.

  22. Khudina, O.G., Shchegol’kov, E.V., Burgart, Ya.V., and Saloutin, V.I., Khimiya i biologicheskaya aktivnost’ sinteticheskikh i prirodnykh soedinenii. Azotsoder-zhashchie geterotsikly (Chemistry and Biological Activity of Synthetic and Natural Compounds. Nitrogen-Containing Heterocycles), Kartsev, V.G., Ed., Moscow: Mezhdunar. Blagotvor. Fond “Nauchnoe Partnerstvo,” 2006, vol. 2, p. 287.

    Google Scholar 

  23. Barmin, M.I. and Mel’nikov, V.V., Novye amino-1,2,4-triazolil-i tetrazolilalkany (New Amino-1,2,4-triazolyl-and Tetrazolylalkanes), St. Petersburg: Sankt-Peterb. Gos. Univ. Tekhnologii i Dizaina, 2002.

    Google Scholar 

  24. Chenard, B.L., Lipinski, C.A., Dominy, B.W., Mena, E.E., Ronau, R.T., Butterfield, G.C., Marinovic, L.C., Pagnozzi, M., Butler, T.W., and Tsang, T., J. Med. Chem., 1990, vol. 33, no. 3, p. 1077.

  25. Blackman, A.J. and Bowie, J.H., Austr. J. Chem., 1972, vol. 25, no. 2, p. 335.

    CAS  Google Scholar 

  26. Katritzky, A.R., Lue, P., and Yannakopoulou, K., Tetrahedron, 1990, vol. 46, no. 2, p. 641.

    Article  CAS  Google Scholar 

  27. Kubota, S. and Uda, M., Chem. Pharm. Bull., 1975, vol. 23, no. 5, p. 955.

    CAS  Google Scholar 

  28. Claramunt, R.M., Sanz, D., Boyer, G., Catalan, J., de Paz, J.L., and Elguero, J., Magn. Reson. Chem., 1993, vol. 31, no. 9, p. 791.

    Article  CAS  Google Scholar 

  29. Györgydeák, Z., Holzer, W., Kunz, R.W., and Linden, A., Monatsh. Chem., 1995, vol. 126, nos. 6–7, p. 733.

    Article  Google Scholar 

  30. Mironova, E.V., Gubaidullin, A.T., Litvinov, I.A., Nabiullin, V.N., and Buzykin, B.I., Acta Crystallogr., Sect. A, 2005, vol. 61, p. 274; Book of Abstracts, XXth Congr. Int. Union Crystallogr., Florence, 2005, P.05.05.1.

    Article  Google Scholar 

  31. Trifonov, R.U., Doctoral (Chem.) Dissertation, St. Patersburg, 2006.

  32. Xue, H., Twamley, B., and Shreeve, J.M., J. Org. Chem., 2004, vol. 69, no. 4, p. 1397.

    Article  CAS  Google Scholar 

  33. Anders, E., Wermann, K., Wiedel, B., and Vanden Ende, J.-J., Liebigs Ann.-Recuel, 1997, no. 4, p. 745.

  34. Chipen, G.I. and Grinshtei, V.Ya., Izv. Akad. Nauk Latv. SSR, Ser. Khim., 1962, no. 4, p. 401; Ref. Zh., Khim.,1995, no. 5 B 91.

  35. Lipatova, E.A., Shokhor, I.N., Lopyrev, V.A., and Pevzner, M.S., Khimiya geterotsiklisheskikh soedinenii. Azotsoderzhashchie geterotsikly (Chemistry of Heterocyclic Compounds. Nitrogen-Containing Heterocycles), Riga: Zinatne, 1967, vol. 1, p. 186.

    Google Scholar 

  36. El Issami, S., Bazzi, L., Hilali, M., Salghi, R., and Kertit, S., Ann. Chim.-Sci. Mat., 2002, vol. 27, no. 4, p. 63.

    Article  Google Scholar 

  37. Chebabe, D., Chikh, Z.A., Hajjaji, N., Srhiri, A., and Zucchi, F., Corros. Sci., 2003, vol. 45, no. 2, p. 309.

    Article  Google Scholar 

  38. Mirzaei, Y.R. and Shreeve, J.M., Synthesis, 2003, no. 1, p. 24.

  39. Panasyuk, O.G. and Shestozub, A.B., Ukrainian Patent no. 64 855, 2004; Ref. Zh., Khim., 2005, no. 19 N 210 P.

  40. Vaidhyanathan, R., Natarajan, S., and Rao, C.N.R., J. Mol. Struct., 2002, vol. 608, nos. 2–3, p. 123.

    Article  CAS  Google Scholar 

  41. Chitra, R., Thiruvenkatam, V., Choudhury, R.R., Hosura, M.V., and Guru Rowb, T.N., Acta Crystallogr., Sect. C: Cryst. Struct. Commun., vol. 62, no. 5, p. 274.

  42. Cambrige Structural Database System. Version 5.27, Cambridge Crystallographic Data Centre, 2006.

  43. Moers, O., Wijaya, K., Jones, P.G., and Blaschette, A., Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1999, vol. 55, no. 5, p. 754.

    Article  Google Scholar 

  44. Kiviniemi, S., Nissinen, M., Lamsa, M.T., Jalonen, J., Rissanen, K., and Pursiainen, J., New J. Chem., 2000, vol. 24, p. 47.

    Article  CAS  Google Scholar 

  45. Bujak, M. and Zaleski, J., Z. Naturforsch., Teil B, 2002, vol. 57, no. 3, p. 157.

    CAS  Google Scholar 

  46. Lynch, D.E., Smith, G., Byriel, K.A., and Kennard, C.H.L., Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1994, vol. 50, no. 8, p. 1291.

    Article  Google Scholar 

  47. Lynch, D.E., Tatif, T., Smith, G., Byriel, K.A., Kennard, C.H.L., and Parsons, S., Aust. J. Chem., 1998, vol. 51, no. 5, p. 403.

    Article  CAS  Google Scholar 

  48. Byriel, K.A., Kennard, C.H.L., Lynch, D.E., Smith, G., and Thompson, J.G., Aust. J. Chem., 1992, vol. 45, no. 6, p. 969.

    CAS  Google Scholar 

  49. Lynch, D.E., Dougall, T., Smith, G., Byriel, K.A., and Kennard, C.H.L., J. Chem. Crystallogr., 1999, vol. 29, no. 1, p. 67.

    Article  CAS  Google Scholar 

  50. Lynch, D.E., Smith, G., Byriel, K.A., Kennard, C.H.L., and Wittaker, A.K., Aust. J. Chem., 1994, vol. 47, no. 2, p. 309.

    CAS  Google Scholar 

  51. Li Jia-Rong, Chen Bo-Ren, Ou Yu-Xiang, Cui Xiu-Shan, and Liu Zuo-Cai, Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1992, vol. 48, no. 8, p. 1540.

    Article  Google Scholar 

  52. Smith, G., Lynch, D.E., Byriel, K.A., and Kennard, C.H.L., Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1996, vol. 52, no. 1, p. 231.

    Article  Google Scholar 

  53. Reck, G. and Just, M., Cryst. Struct. Commun., 1982, vol. 11, p. 1857.

    CAS  Google Scholar 

  54. Wen Dong, Ya-Qiu Sun, Bin Yu, Zhou Hui-Bo, Song Hai-Bin, Liu Zhan-Quan, Wang Qing-Mei, Liao Dai-Zheng, Jiang Zong-Hu, Yan Shi-Ping, and Cheng Peng, New J. Chem., 2004, vol. 28, no. 11, p. 1347.

    Article  CAS  Google Scholar 

  55. Seccombe, R.C. and Kennard, C.H.L., J. Chem. Soc., Perkin Trans. 2, 1973, no. 1, p. 1.

  56. Werner, P.-E., Cryst. Struct. Commun., 1977, vol. 6, p. 69.

    CAS  Google Scholar 

  57. Germain, G., Declercq, J.P., Van Meerssche, M., Hervens, F., Viehe, H.G., and Michel, A., Bull. Soc. Chim. Belg., 1975, vol. 84, no. 10, p. 1005.

    CAS  Google Scholar 

  58. Allen, F.H., Kennard, O., Watson, D.G., Brammer, L., Orpen, A.G., and Taylor, R., J. Chem. Soc., Perkin Trans. 2, 1987, no. 1, p. S1.

  59. Atkinson, M.R. and Polya, B., J. Chem. Soc., 1954, no. 10, p. 3319.

  60. Straver, L.H. and Schierbeek, A.J., MolEN. Structure Determination System, Delft, the Netherlands: Nonius B.V., 1994, vols. 1–2.

    Google Scholar 

  61. Altomare, A., Cascarano, G., Giacovazzo, C., and Viterbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47, no. 4, p. 744.

    Article  Google Scholar 

  62. Sheldrick, G.M., SHELX-97. Programs for Crystal Structure Analysis (Release 97-2), Gottingen, Germany: University of Gottingen, 1997.

    Google Scholar 

  63. Farrugia, L.J., J. Appl. Crystallogr., 1999, vol. 32, no. 3, p. 837.

    Article  Google Scholar 

  64. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46, no. 1, p. 34.

    Google Scholar 

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  1. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences, ul. Arbuzova 8, Kazan, 420088, Tatarstan, Russia

    B. I. Buzykin, E. V. Mironova, V. N. Nabiullin, N. M. Azancheev, L. V. Avvakumova, I. Kh. Rizvanov, A. T. Gubaidullin, I. A. Litvinov & V. V. Syakaev

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  1. B. I. Buzykin
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Original Russian Text © B.I. Buzykin, E.V. Mironova, V.N. Nabiullin, N.M. Azancheev, L.V. Avvakumova, I.Kh. Rizvanov, A.T. Gubaidullin, I.A. Litvinov, V.V. Syakaev, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 3, pp. 476–494.

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Buzykin, B.I., Mironova, E.V., Nabiullin, V.N. et al. Tautomerism of aza cycles: II. Synthesis and structure of 5-substituted 3-(2-hydroxyethylsulfanyl)-1H-1,2,4-triazoles and their salts. Preference of the 1H,4H-1,2,4-triazolium tautomers. Russ J Gen Chem 78, 461–479 (2008). https://doi.org/10.1134/S1070363208030225

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