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Tautomerism of aza cycles: I. Structure of 3(5)-butylsulfanyl-5(3)-methyl(phenyl)-1H-1,2,4-triazole tautomers in crystal. Preference of the 3-RA-5-RD-1H-tautomer of 3(5)-mono-and 3,5-disubstituted 1,2,4-triazoles

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Abstract

The X-ray diffraction study of potentially tautomeric 3(5)-butylsulfanyl-5(3)-methyl-1H-1,2,4-triazole and its 5(3)-phenyl-substituted analog showed that these compounds in crystal have the structure of 3-butylsulfanyl-5-methyl(phenyl)-1H-tautomers. Analysis of our experimental and published data indicated that 3(5)-monosubstituted 1,2,4-triazoles and 3,5-disubstituted derivatives having nonequivalent substituents in crystal as exist as a tautomer in which the electron-acceptor substituent (RA) occupies the 3 position, while the electron-donor substituent (RD) resides in the 5 position, i.e., as 3-RA-5-RD-1H-1,2,4-triazoles. Symmetric 3,5-disubstituted 1,2,4-triazoles could give rise to tautomeric equilibrium between the 1H-and 2H-structures even in crystal.

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References

  1. Katritskii, A.R., Usp. Khim., 1972, vol. 41, no. 4, p. 700.

    Google Scholar 

  2. Elguero, J., Mazzain, C., Katritzky, A.R., and Linda, P., Adv. Heterocycl. Chem., Suppl. 1, 1976, p. 266.

  3. Elguero, J., Katritzky, A.R., and Denisko, O.V., Adv. Heterocycl. Chem., 2000, vol. 76, p. 1.

    CAS  Google Scholar 

  4. Minkin, V.I., Garnovskii, A.D., and Elguero, J., Adv. Heterocycl. Chem., 2000, vol. 76, p. 157.

    CAS  Google Scholar 

  5. Claramunt, R.M., Elguero, J., and Katritzky, A.R., Adv. Heterocycl. Chem., 2000, vol. 77, p. 1.

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  7. Bagal, L.I. and Pevzner, M.S., Khim. Geterotsikl. Soedin., 1970, no. 4, p. 558.

  8. Sainsbury, M., Rodd’s Chemistry of Carbon Compounds, Ansell, M.F., Ed., Amsterdam: Elsevier, vol. IV, part D, pp. 32–56.

  9. Pevzner, M.S., Kofman, T.P., and Gorbunova, N.N., Zh. Org. Khim., 1978, vol. 14, no. 10, p. 2024.

    CAS  Google Scholar 

  10. Litchman, W.M., J. Heterocycl. Chem., 1982, vol. 19, no. 5, p.1235.

    CAS  Google Scholar 

  11. Sorescu, D.C., Bennett, C.M., and Thompson, D.L., J. Phys. Chem. A, 1998, vol. 102, no. 50, p. 10348.

    Article  CAS  Google Scholar 

  12. Claramunt, R.M., Lopez, C., Garcia, M.A., and Otero, M.D., New J. Chem., 2001, vol. 25, p. 1061.

    Article  CAS  Google Scholar 

  13. Kelarev, V.I., Shvekhgeimer, G.A., and Lunin, A.F., Khim. Geterotsikl. Soedin., 1984, no. 9, p. 1271.

  14. Alekseeva, V.Ya., Boikov, Yu.A., Viktorovskii, I.V., and V’yunov, K.A., Khim. Geterotsikl. Soedin., 1986, no. 11, p. 1553.

  15. Maretina, I.A., Russ. J. Org. Chem., 2005, vol. 41, no. 1, p. 1.

    Article  CAS  Google Scholar 

  16. Lipson, V.V., Desenko, S.M., Borodina, V.V., Shirobokova, M.G., and Musatov, V.I., Russ. J. Org. Chem., 2005, vol. 41, no. 1, p. 114.

    Article  CAS  Google Scholar 

  17. Chudinov, M. V., Konstantinova, I.D., and Ryzhova, O.I., Khim.-Farm. Zh., 2005, vol. 39, no. 4, p. 43.

    Google Scholar 

  18. Tartakovskii, V.A., Frumkin, A.E., Churakov, A.M., and Strelenko, Yu.A., Izv. Ross. Akad. Nauk, Ser. Khim., 2005, no. 3, p. 706.

  19. Makarskii, V.V., Zubkov, V.L., Lopyrev, V.A., and Voronkov, M.G., Khim. Geterotsikl. Soedin., 1977, no. 4, p. 540.

  20. Ostrovskii, V.A., Erusalimskii, G.B., and Shcherbinin, M.B., Russ. J. Org. Chem., 1995, vol. 31, no. 9, p. 1284.

    Google Scholar 

  21. Pevzner, M.S., Fedorova, E.Ya., Shokhor, N.N., and Bagal, L.I., Khim. Geterotsikl. Soedin., 1971, no. 2, p. 275.

  22. Creagh, L.T. and Truitt, P., J. Org. Chem., 1968, vol. 33, no. 7, p. 2956.

    CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  24. Claramunt, R.M., Sanz, D., and Lopez, C., Magn. Reson. Chem., 1997, vol. 35, no. 1, p. 35.

    Article  CAS  Google Scholar 

  25. Katritzky, A.R. and Pozharskii, A.F., Handbook of Heterocyclic Chemistry, Amsterdam: Elsevier, 2000, 2nd ed.

    Google Scholar 

  26. Trzhtsinskaya, B.V., Kositsina, E.I., and Pertsikov, B.Z., Khim. Geterotsikl. Soedin., 1987, no. 2, p. 271.

  27. Jemenez-Cruz, F., Hernandez-Ortega, S., and Ros-Olivares, H., J. Mol. Struct., 2003, vol. 650, no. 1, p. 223.

    Article  CAS  Google Scholar 

  28. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs), Khar’kov: Torsing, 1997, vol. 2.

    Google Scholar 

  29. Papakonstantinougaroufalia, S.S., Tani, E., and Todoulou, O., J. Pharm. Pharmacol., 1998, no. 1, p. 117.

  30. Meshcheryakov, V.I. and Vereshchagin, L.I., VICh/SPID Rodstv. Probl., 1998, no. 2, p. 68.

  31. Xu, L.-Z., Zhang, S.-S., Li, H.-J., and Jiao, K., Chem. Res. Chin. Univ., 2002, vol. 18, no. 3, p. 284.

    Google Scholar 

  32. Chorab, M.M., El-Sharief, A.M.Sh., and Ammar, J.A., Phosphorus Sulfur Silicon Relat. Elem., 2001, vol. 173, p. 223.

    Google Scholar 

  33. Selezneva, E.S., Belousova, Z.P., and Ten-gaev, E.I., Khim.-Farm. Zh., 2003, vol. 37, no. 8, p. 14.

    Google Scholar 

  34. Chu, C.H., Zhang, Y., and Zhang, Z.Y., Indian J. Chem., Sect. B, 2000, vol. 39, no. 10, p. 791.

    Google Scholar 

  35. Navidpour, L., Karimi, L., and Amini, M., J. Heterocycl. Chem., 2004, vol. 41, no. 2, p. 201.

    CAS  Google Scholar 

  36. Song, C.E., Kim, J.H., Choi, J.H., and Jin, B.W., Heterocycles, 1999, vol. 51, no. 1, p. 161.

    CAS  Google Scholar 

  37. Trzhtsinskaya, B.V., Skvortsova, G.G., Mansurov, Yu.A., and Buchin, P.I., Khim.-Farm. Zh., 1982, vol. 16, no. 12, p. 58.

    Google Scholar 

  38. Hoggarth, E., J. Chem. Soc., 1949, no. 5, p. 1160.

  39. Labanauskas, L., Kal’tsas, V., Udrenaite, E., Buchinskaite, V., Brukshtus, A., and Susvilo, I., Azotistye geterotsikly i alkaloidy (Nitrogen-Containing Heterocycles and Alkaloids), Kartsev, V.G. and Tolstikov, G.A., Eds., Moscow: Iridium, 2001, vol. 2, p. 181.

    Google Scholar 

  40. Tolstyakov, V.V. and Tselinskii, I.V., Russ. J. Gen. Chem., 2004, vol. 74, no. 3, p. 399.

    Article  CAS  Google Scholar 

  41. Oprean, L., David, L., and Zaharia, V., Stud. Univ. Babes-Bolyai. Chem., 2002, vol. 47, no. 1, p. 179; Ref. Zh. Khim., 2004, no. 9V85.

    CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    CAS  Google Scholar 

  45. Chenard, B.L., Lipinski, C.A., and Dominy, B.W., J. Med. Chem., 1990, vol. 33, no. 3, p. 1077.

    Article  CAS  Google Scholar 

  46. Heravi, M.M., Montazeri, N., and Rahimizageh, M., Monatsh. Chem., 2001, vol. 132, no. 10, p. 1225.

    CAS  Google Scholar 

  47. Goldstein, P., Ladell, J., and Abowitz, G., Acta Crystallogr., Sect. B, 1969, vol. 25, no. 1, p. 135.

    Article  CAS  Google Scholar 

  48. Deutschl, H., Ber. Bunsenges. Phys. Chem., 1965, vol. 69, no. 6, p. 550; Ref. Zh., Khim., 1966, no. 12B452.

    Google Scholar 

  49. Chiang, J.F. and Lu, K.C., J. Mol. Struct., 1977, vol. 41, no. 2, p. 223.

    Article  CAS  Google Scholar 

  50. Jeffrey, G.A., Ruble, J.R., and Yates, J.H., Acta Crystallogr., Sect. B, 1983, vol. 39, p. 388.

    Article  Google Scholar 

  51. Starova, G.L., Frank-Kamenetskii, O.V., Makarskii, V.V., and Lopyrev, V.A., Kristallografiya, 1978, vol. 23, no. 4, p. 849.

    CAS  Google Scholar 

  52. Evrard, G., Durant, F., and Michel, A., Bull. Soc. Chim. Belg., 1984, vol. 93, no. 3, p. 233.

    Article  CAS  Google Scholar 

  53. Delage, C., Lagorce, J.-F., and Raby, C., Acta Crystallogr., Sect. C., 1988, vol. 44, no. 12, p. 2187.

    Article  Google Scholar 

  54. Nieuwenhuyzen, M., Keirse, R., Shaw, B., and Vos, J.G., Acta Crystallogr., Sect. C, 1999, vol. 55, no. 2, p. 264.

    Article  Google Scholar 

  55. Aouial, M., Viallefont, P., and Ammari, L.El., Acta Crystallogr., Sect. C, 1991, vol. 47, no. 9, p. 1866.

    Article  Google Scholar 

  56. Garcia, E. and Lee, K.-Y., Acta Crystallogr., Sect. C, 1992, vol. 48, no. 9, p. 1682.

    Article  Google Scholar 

  57. Borbulevych, O.Ya., Shishkin, O.V., and Desenko, S.M., Acta Crystallogr., Sect. C, 1998, vol. 54, no. 3, p. 442.

    Article  Google Scholar 

  58. Nikitina, E.V., Starova, G.L., Frank-Kamenets-kaya, O.V., and Pevzner, M.S., Kristallografiya, 1982, vol. 27, no. 3, p. 485.

    CAS  Google Scholar 

  59. Rusinov, V.L., Pilicheva, T.L., and Tumashev, A.A., Khim. Geterotsikl. Soedin., 1990, no. 12, p. 1632.

  60. Wawrzycka, I., Koziol, A.E., and Walesa, K.G., Z. Kristallogr., 2000, vol. 215, no. 12, p. 766.

    Article  CAS  Google Scholar 

  61. Prins, R., Birker, P.J.M.W.L., and Verschoor, G.C., Acta Crystallogr., Sect. B, 1982, vol. 38, no. 11, p. 2934.

    Article  Google Scholar 

  62. Starova, G.L., Frank-Kamenetskaya, O.V., and Shibanova, E.F., Kristallografiya, 1980, vol. 25, no. 6, p. 1292.

    CAS  Google Scholar 

  63. Bradshaw, J.S., Nielsen, R.B., and Tse, P.-K., J. Heterocycl. Chem., 1986, vol. 23, p. 361.

    Article  CAS  Google Scholar 

  64. Siedle, A.R., Webb, R.J., and Newmark, R.A., J. Fluorine Chem., 2003, vol. 122, no. 2, p. 175.

    Article  CAS  Google Scholar 

  65. Nieuwenhuyzen, M., Keyes, T.E., Gallagher, J.F., and Vos, J.G., Acta Crystallogr., Sect. C, 1997, vol. 53, no. 12, p. 1873.

    Article  Google Scholar 

  66. Starova, G.L., Frank-Kamenetskaya, O.V., and Makarskii, V.V., Kristallografiya, 1990, vol. 35, no. 3, p. 769.

    CAS  Google Scholar 

  67. Ried, W., Broft, G.W., and Bats, J.W., Chem. Ber., 1983, vol. 116, no. 4, p. 1547.

    CAS  Google Scholar 

  68. Kalman, A. and Argay, G., J. Mol. Struct., 1983, vol. 102, p. 391.

    Article  CAS  Google Scholar 

  69. Wawrzycka-Gorczyca, J., Rzeszotarska, B., and Dzygiel, A., Z. Kristallogr., 2003, vol. 218, no. 7, p. 480.

    Article  CAS  Google Scholar 

  70. Yazici, S., Tsik, S., and Agar, E., Acta Crystallogr., Sect. E, 2004, vol. 60, no. 5, p. 815.

    Article  CAS  Google Scholar 

  71. Matveev, Yu.I., Gorbatenko, V.I., and Samarai, L.I., Zh. Org. Khim., 1988, vol. 24, no. 10, p. 2216.

    CAS  Google Scholar 

  72. Kuroda, R., Sanderson, M.R., Neidle, S., and Reese, C.B., J. Chem. Soc., Perkin Trans. 2, 1982, no. 5, p. 617.

  73. Hata, T., Furukawa, Y., Konosu, T., and Oida, S., Bull. Chem. Soc. Jpn., 1991, vol. 64, no. 10, p. 2877.

    Article  CAS  Google Scholar 

  74. Starova, G.L., Frank-Kamenetskaya, O.V., and Pevzner, M.S., Zh. Strukt. Khim., 1988, vol. 29, no. 5, p. 162.

    CAS  Google Scholar 

  75. Cotrait, M., Acta Crystallogr., Sect. C, 1986, vol. 42, no. 10, p. 1437.

    Article  Google Scholar 

  76. Rodier, N., Robert, J.-M., and leBaut, G., Acta Crystallogr., Sect. C, 1993, vol. 49, no. 1, p. 161.

    Article  Google Scholar 

  77. Bednarek, E., Modzelewska-Banachiewicz, B., and Cyranski, M.K., J. Mol. Struct., 2001, vol. 562, p. 167.

    Article  CAS  Google Scholar 

  78. Cingi, M.B., Lanfranchi, M., and Pellinghelli, M.A., Eur. J. Inorg. Chem., 2000, no. 4, p. 703.

  79. Bois, C., Philoche-Levisalles, M., and Chihaoui, M., J. Heterocycl. Chem., 1983, vol. 20, no. 1, p. 97.

    Article  CAS  Google Scholar 

  80. Palmer, M.H. and Parsons, S., Acta Crystallogr., Sect. C, 1996, vol. 52, no. 11, p. 2818.

    Article  Google Scholar 

  81. Carlsen, P.H.J., Jorgensen, K.B., and Gautun, O.R., Acta Chem. Scand., 1995, vol. 49, p. 676.

    Article  CAS  Google Scholar 

  82. Virovets, A.V., Lider, E.V., and Elokhina, V.N., Zh. Strukt. Khim., 2005, vol. 46, no. 2, p. 366.

    Google Scholar 

  83. Zhu, D.-R., Xu, Y., and Zhang, Y., Acta Crystallogr., Sect. C, 2000, vol. 56, no. 7, p. 895.

    Article  Google Scholar 

  84. Starova, G.L., Frank-Kamenetskaya, O.V., and Pevzner, M.S., Vestn. Leningr. Gos. Univ., Ser. 4, 1991, issue 2, no. 11, p. 103.

  85. Ciunik, Z., Drabent, K., and Szterenberg, L., J. Mol. Struct., 2002, vol. 641, no. 2, p. 175.

    Article  CAS  Google Scholar 

  86. Dupont, L., Dideberg, O., and Jamoulle, J.C., Acta Crystallogr., Sect. C, 1984, vol. 40, no. 7, p. 1269.

    Article  Google Scholar 

  87. Han, L., Zhou, Y.-F., and Wang, R.-H., Acta Crystallogr., Sect. E, 2004, vol. 60, no. 5, p. 813.

    Article  CAS  Google Scholar 

  88. Mrozek, A., Karolak-Wojciechowska, J., Amiel, P., and Barbe, J., J. Mol. Struct., 2000, vol. 524, p. 151.

    Article  CAS  Google Scholar 

  89. Allen, F.H., Acta Crystallogr., Sect. B, 2002, vol. 58, p. 380.

    Article  CAS  Google Scholar 

  90. Vereshchagin, A.N., Induktivnyi effekt. Konstanty zamestitelei dlya korrelyatsionnogo analiza (Inductive Effect. Substituent Constants for Correlation Analysis), Moscow: Nauka, 1988.

    Google Scholar 

  91. Allen, F.H., Kennard, O., Watson, D.G., Brammer, L., Orpen, A.G., and Taylor, R., J. Chem. Soc., Perkin Trans. 2, 1987, no. 12, p. S1.

  92. Kitaigorodskii, A.I., Molekulyarnye kristally (Molecular Crystals), Moscow: Nauka, 1971.

    Google Scholar 

  93. Gubaidullin, A.T., Mamedov, V.A., and Litvinov, I.A., ARKIVOC, 2004, Part XII, p. 80.

  94. Gubaidullin, A.T., Beskrovnyi, D.V., and Litvinov, I.A., Zh. Strukt. Khim., 2005, vol. 46Suppl., p. S191.

    Google Scholar 

  95. Charton, M., J. Org. Chem., 1965, vol. 30, no. 10, p. 3346.

    CAS  Google Scholar 

  96. Krüger, C.-F. and Freiberg, W., Z. Chem., 1965, vol. 5, no. 5, p. 381.

    Google Scholar 

  97. Lopyrev, V.A., Larina, L.I., and Vakul’skaya, T.I., Usp. Khim., 1986, vol. 55, no. 5, p. 769.

    CAS  Google Scholar 

  98. Hansch, C., Leo, A., and Taft, R.W., Chem. Rev., 1991, vol. 91, no. 2, p. 165.

    Article  CAS  Google Scholar 

  99. Datta, D., J. Phys. Org. Chem., 1991, vol. 4, no. 2, p. 96.

    Article  CAS  Google Scholar 

  100. Cherkasov, A.R., Galkin, V.I., Sibgatullin, I.M., and Cherkasov, R.A., Russ. J. Org. Chem., 1997, vol. 33, no. 9, p. 1243.

    CAS  Google Scholar 

  101. Brovarets, V.S., Golovchenko, A.V., Sviripa, V.N., Zyuz’, K.B., Chernega, A.N., and Drach, B.S., Russ. J. Gen. Chem., 2004, vol. 74, no. 9, p. 1328.

    Article  CAS  Google Scholar 

  102. Kereselidze, Dzh.A., Zarkua, T.Sh., and Kikalishvili, T.Dzh., Usp. Khim., 2002, vol. 71, no. 12, p. 1120.

    Google Scholar 

  103. Lebedev, A.V., Lebedeva, A.B., Sheludyakov, V.D., Kovaleva, E.A., Ustinova, O.L., and Kozhevnikov, I.B., Russ. J. Gen. Chem., 2005, vol. 75, no. 5, p. 782.

    Article  CAS  Google Scholar 

  104. Nikulin, V.V., Artamonova, T.V., and Koldobskii, G.I., Russ. J. Org. Chem., 2005, vol. 41, no. 3, p. 444.

    Article  CAS  Google Scholar 

  105. Buzykin, B.I., Lipunova, G.N., Sysoeva, L.N., and Rusinova, L.I., Formazany (Formazans), Moscow: Nauka, 1992.

    Google Scholar 

  106. Tertov, B.A., Burykin, V.V., and Koblik, A.V., Khim. Geterotsikl. Soedin., 1972, no. 11, p. 1552.

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

    Article  Google Scholar 

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

    Google Scholar 

  109. Sheldrick, G.M., SHELX-97. Programs for Crystal Structure Analysis (Release 97-2), Göttingen: Univ. of Göttingen, Germany.

  110. 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, A. T. Gubaidullin & I. A. Litvinov

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Original Russian Text © B.I. Buzykin, E.V. Mironova, V.N. Nabiullin, A.T. Gubaidullin, I.A. Litvinov, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 9, pp. 1534–1550.

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Buzykin, B.I., Mironova, E.V., Nabiullin, V.N. et al. Tautomerism of aza cycles: I. Structure of 3(5)-butylsulfanyl-5(3)-methyl(phenyl)-1H-1,2,4-triazole tautomers in crystal. Preference of the 3-RA-5-RD-1H-tautomer of 3(5)-mono-and 3,5-disubstituted 1,2,4-triazoles. Russ J Gen Chem 76, 1471–1486 (2006). https://doi.org/10.1134/S1070363206090209

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