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Synthesis and structure of 1-tert-butyl-substituted 3(5)-alkylpyrazoles from 2-chlorovinyl ketones

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Abstract

Reactions of alkyl, halomethyl 2-chlorovinyl ketones with tert-butylhydrazine in the presence of triethylamine afford unsymmetrical 1-(tert-butyl)-3- and -5-disubstituted pyrazoles. The reaction direction is governed by the ketone ability of the nucleophilic substitution of chlorine and of the dehydrochlorination leading to acetylene ketones. 2-Chlorovinyl ketones react with tert-butylhydrazine along two routes giving mixtures of 1-(tert-butyl)-3- and -5-alkylpyrazoles. The content of 3-alkyl-1-(tert-butyl)pyrazole in the formed isomers mixture grows up to 73% with growing length of the alkyl chain of the ketone and up to 87 and 94% at introducing halogen atom in the alkyl fragment of the chloroenone.

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References

  1. Elguero, J., Goya, P., Jagerovic, N., and Silva, A.M.S., Targets Heterocycl. Syst., 2002, vol. 6, p. 53.

    Google Scholar 

  2. Pérez-Fernández, R., Goya, P., and Elguero, J., Arkivoc, 2014, vol. ii, p. 233.

    Google Scholar 

  3. Fustero, S., Sanchez-Rosello, M., Barrio, P., and Simon-Fuentes, A., Chem. Rev., 2011, vol. 111, p. 6984.

    Article  CAS  Google Scholar 

  4. Janin, Y.L., Chem. Rev., 2012, vol. 112, p. 3924.

    Article  CAS  Google Scholar 

  5. Pizzuti, L., Barschak, A.G., Stefanello, F.M., Farias, M.D., Lencina, C., Roesch-Ely, M., Cunico, W., Moura, S., and Pereira, C.M.P., Curr. Org. Chem., 2014, vol. 18, p. 115.

    Article  CAS  Google Scholar 

  6. Vicentini, C.B., Romagnoli, C., Andreotti, E., and Mares, D., J. Agric. Food Chem., 2007, vol. 55, p. 10331.

    Article  CAS  Google Scholar 

  7. Li, Y., Zhang, H.-Q., Liu, J., Yang, X.-P., and Liu, Z.-J.J., J. Agric. Food Chem., 2006, vol. 54, p. 3636.

    Article  CAS  Google Scholar 

  8. Shiga, Y., Okada, I., and Fukuchi, T., J. Pesticide Sci., 2003, vol. 28, p. 313.

    Article  CAS  Google Scholar 

  9. Grapov, A.F., Russ. Chem. Rev., 1999, vol. 68, p 697.

    Article  CAS  Google Scholar 

  10. Chang, E.-M., Lee, C.-T., Chen, C.-Y., Wong, F.F., and Yeh, M.-Y., Aust. J. Chem., 2008, vol. 61, p. 342.

    Article  CAS  Google Scholar 

  11. Han, L.M. and Timmons, R.B., Chem. Mater., 1998, vol. 10, p. 1422.

    Article  CAS  Google Scholar 

  12. Shatalov, G.V., Preobrazhenskii, S.A., and Kuznetsov, V.A., Izv. Vuzov, Ser. Khim. I Khim. Tekhnol., 1999, vol. 42, p. 62.

    CAS  Google Scholar 

  13. Cavero, E., Uriel, S., Romero, P., Serrano, J.L., and Giménez, R., J. Am. Chem. Soc., 2007, vol. 129, p. 11608.

    Article  CAS  Google Scholar 

  14. Ye, C., Gard, G.L., Winter, R.W., Syvret, R.G., Twamley, B., and Shreeve, J.M., Org. Lett., 2007, vol. 9, p. 3841.

    Article  CAS  Google Scholar 

  15. Ojwach, S.O. and Darkwa, G.L., J. Inorg. Chim. Acta, 2011, vol. 363, p. 1947.

    Article  Google Scholar 

  16. Potapov, A.S., Domnina, G.A., Petrenko, T.V., and Khlebnikov, A.I., Polyhedron, 2012, vol. 33, p. 150.

    Article  CAS  Google Scholar 

  17. Ovcharenko, V.I., Maryunina, K.Yu., Fokin, S.V., Tretyakov, E.V., Romanenko, G.V., and Ikorskii, V.N., Russ. Chem. Bull., 2004, vol. 53, p. 2406.

    Article  CAS  Google Scholar 

  18. Fokin, S., Ovcharenko, V., Romanenko, G., and Ikorskii, V., Inorg. Chem., 2004, vol. 43, p. 969.

    Article  CAS  Google Scholar 

  19. Pohland, A.E. and Benson, W.R., Chem. Rev., 1966, vol. 66, p. 161.

    Article  CAS  Google Scholar 

  20. Kochetkov, N.K., Usp. Khim., 1955, vol. 24, p. 32.

    CAS  Google Scholar 

  21. Levkovskaya, G.G., Bozhenkov, G.V., and Mirskova, A.N., Izbrannye metody sinteza i modifikatsii geterotsiklov (Selected Methods of Synthesis and Modification of Heterocycles), Kartsev, V.G., Ed., Moscow: IBS PRESS, 2003, vol. 2.

  22. Kaberdin, R.V., Potkin, V.I., and Petkevich, S.K., Izv. National Akad. Nauk Belarusi, Ser. Khim. Nauk, 2006, p. 100.

    Google Scholar 

  23. Moiseev, I.K., Makarova, N.V., and Zemtsova, M.N., Izv. Vuzov, Ser. Khim. I Khim. Tekhnol., 2007, vol. 50, p. 3.

    Google Scholar 

  24. Bozhenkov, G.V., Levkovskaya, G.G., Mirskova, A.N., Dolgushin, G.V., Larina, L.N., and Ushakov, P.E., Russ. J. Org. Chem., 2003, vol. 39, p. 1069.

    Article  CAS  Google Scholar 

  25. Levkovskaya, G.G., Bozhenkov, G.V., Larina, L.I., and Mirskova, A.N., Russ. J. Org. Chem., 2002, vol. 38, p. 1501.

    Article  CAS  Google Scholar 

  26. Levkovskaya, G.G., Bozhenkov, G.V., Mirskova, A.N., and Tantsyrev, A.P., RF Patent 2186772, 2002; Byull. Izobret., 2002, no. 22.

  27. Ichikava, J., Kobayashi, M., Noda, Y., Yokota, N., Amano, K., and Minami, T., J. Org. Chem., 1996, vol. 61, p. 2763.

    Article  Google Scholar 

  28. Beltrán-Rodil, S., Edwards, M.G., Pugh, D.S., Reid, M., and Taylor, R.K., Synlett., 2010, p. 602.

    Google Scholar 

  29. Levkovskaya, G.G., Kobelevskaya, V.A., Rudyakova, E.V., Ha, Q.Kh., Samultsev, D.O., and Rozentsveig, I.B., Tetrahedron, 2011, vol. 67, p. 1844.

    Article  CAS  Google Scholar 

  30. Ioffe, B.V. and Zelenina, N.L., Chem. Heterocycl. Comp., 1970, vol. 6, p. 1321.

    Article  Google Scholar 

  31. Levkovskaya, G.G., Bozhenkov, G.V., Malyushenko, R.N., and Mirskova, A.N., Russ. J. Org. Chem., 2001, vol. 37, p. 1795.

    Article  CAS  Google Scholar 

  32. Grandberg, I.I., Chem. Heterocycl. Comp., 1965, vol. 1, p. 184.

    Article  Google Scholar 

  33. Bozhenkov, G.V., Savosik, V.A., Klyba, L.V., Zhanchipova, E.R., Mirskova, A.N., and Levkovskaya, G.G., Russ. J. Org. Chem., 2008, vol. 44, p. 1194.

    Article  CAS  Google Scholar 

  34. Bozhenkov, G.V., Savosik, V.A., Larina, L.I., Klyba, L.V., Zhanchipova, E.R., Mirskova, A.N., and Levkovskaya, G.G., Russ. J. Org. Chem., 2008, vol. 44, p. 1014.

    Article  CAS  Google Scholar 

  35. Martins, M.A.P., Marzari, M.R.B., Frizzo, C.P., Zanatta, M., Buriol, L., Andrade, V.P., Zanatta, N., and Bonacorso, H.G., Eur. J. Org. Chem., 2012, p. 7112.

    Google Scholar 

  36. Frizzo, C.P., Marzari, M.R.B., Buriol, L., Moreira, D.N., Rosa, F.A., Vargas, P.S., Zanatta, N., Bonacorso, H.G., and Martins, M.A.P., Catal. Commun., 2009, vol. 10, p. 1967.

    Article  CAS  Google Scholar 

  37. Rosa, F.A., Machado, P., Vargas, P.S., Bonacorso, H.G., Zanatta, N., and Martins, M.A.P., Synlett., 2008, p. 1673.

    Google Scholar 

  38. Nesmeyanov, A.N., Kochetkov, N.K., and Rybinskaya, M.I., Izv. Akad. Nauk USSR, Ser. Khim., 1950, p. 350.

    Google Scholar 

  39. Fustero, S., Román, R., Sanz-Cervera, J.F., Simón-Fuentes, A., Cuñat, A.A., Villa Nova, S., and Murguía, M., J. Org. Chem., 2008, vol. 73, p. 3523.

    Article  CAS  Google Scholar 

  40. Habraken, C.L. and Moore, J.A., J. Org. Chem., 1965, vol. 30, p. 1892.

    Article  CAS  Google Scholar 

  41. Bax, A. and Subramanian, S., J. Magn. Res., 1986, vol. 67, p. 565.

    CAS  Google Scholar 

  42. Bax, A. and Subramanian, S., J. Am. Chem. Soc., 1986, vol. 108, p. 2093.

    Article  CAS  Google Scholar 

  43. Atavin, A.S., Levkovskaya, G.G., and Mirskova, A.N., Zh. Org. Khim., 1973, vol. 9, p. 318.

    CAS  Google Scholar 

  44. Hasaninejad, A., Zare, A., Sharghi, H., and Shekouhy, M., Arkivoc, 2008, vol. 11, p. 64.

    Article  Google Scholar 

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Authors and Affiliations

  1. Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk, 664033, Russia

    V. A. Kobelevskaya, L. I. Larina, A. V. Popov, E. V. Rudyakova & G. G. Levkovskaya

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  1. V. A. Kobelevskaya
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  2. L. I. Larina
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  3. A. V. Popov
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  4. E. V. Rudyakova
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  5. G. G. Levkovskaya
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Correspondence to G. G. Levkovskaya.

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Original Russian Text © V.A. Kobelevskaya, L.I. Larina, A.V. Popov, E.V. Rudyakova, G.G. Levkovskaya, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 2, pp. 242–249.

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Kobelevskaya, V.A., Larina, L.I., Popov, A.V. et al. Synthesis and structure of 1-tert-butyl-substituted 3(5)-alkylpyrazoles from 2-chlorovinyl ketones. Russ J Org Chem 51, 231–239 (2015). https://doi.org/10.1134/S1070428015020177

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  • DOI: https://doi.org/10.1134/S1070428015020177

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