Chemistry of Heterocyclic Compounds

, Volume 45, Issue 5, pp 595–605 | Cite as

Reaction of esters of 2-arylcyclo-propanecarboxylic acids with nitrous acid. Synthesis of aryl-substituted 3-ethoxycarbonyl-4,5-dihydroisoxazoles and 3-ethoxycarbonylisoxazoles

  • A. Z. Kadzhaeva
  • E. V. Trofimova
  • A. N. FedotovEmail author
  • K. A. Potekhin
  • R. A. Gazzaeva
  • S. S. Mochalov
  • N. S. Zefirov

Esters of 2-arylcyclopropanecarboxylic acids react with nitrous acid generated in situ with regioselective insertion of the nitrosyl cation into the cyclopropane ring. Depending on the substrate/nitrosylating agent ratio, the reaction proceeds with the formation of either aryl-substituted 3-ethoxycarbonyl-4,5-dihydroisoxazoles or the corresponding isoxazoles. The nature and position of the substituents in the aromatic ring of the starting 2-arylcyclopropanecarboxylic acid esters affect the reaction rate but have no effect on the regioselectivity of the attack by the nitrosyl cation on the three-membered ring. A dependence of the reactivity of isomeric substrates on their stereochemistry and position of the nitro group in the aromatic ring is noted for 2- and 4-nitrophenyl derivatives of esters of cis- and trans-2-arylcyclopropanecarboxylic acids.


5-aryl-3-ethoxycarbonyl-4,5-dihydroisoxazoles 5-aryl-3-ethoxycarbonylisoxazoles ethyl esters of 2-arylcyclopropanecarboxylic acids insertion of the nitrosyl cation into the cyclopropane ring 


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  1. 1.
    T. Tatee, S. Kurashige, A. Shiozawa, K. Narita, M. Takei, S. Ito, H. Migazaki, H. Yamanaka, M. Mirugaki, T. Sakamado, and H. Fukada, Chem. Pharm. Bull., 34, 1634 (1986).Google Scholar
  2. 2.
    V. Venkateshwarlu, A. Krishnamurthy, and C. J. Rao, Indian J. Chem., 27B, 565 (1989).Google Scholar
  3. 3.
    B. H. Lipshutz, Chem. Rev., 86, 795 (1986).CrossRefGoogle Scholar
  4. 4.
    P. G. Baraldi, A. Barco, S. Benetti, G. P. Pollini, and D. Simoni, Synthesis, 857 (1987).Google Scholar
  5. 5.
    P. A. Wade and J. F. Beremak, J. Org. Chem., 52, 2973 (1987).CrossRefGoogle Scholar
  6. 6.
    D. P. Curran, S. A. Scanga, and C. J. Fenk, J. Org. Chem., 49, 3474 (1984).CrossRefGoogle Scholar
  7. 7.
    Yu. S. Shabarov, L. G. Saginova, and R. A. Gazzaeva, Khim. Geterotsikl. Soedin., 738 (1983). [Chem. Heterocycl. Comp., 19, 589 (1983)].Google Scholar
  8. 8.
    S. S. Mochalov, Ya. I. Kuz’min, A. N. Fedotov, E. V. Trofimova, R. A. Gazzaeva, Yu. S. Shabarov, and N. S. Zefirov, Zh. Org. Khim., 34, 1379 (1998).Google Scholar
  9. 9.
    O. B. Bondarenko, A. Yu. Gavrilova, L. G. Saginova, N. V. Zyk, and N. S. Zefirov, Izv. Akad. Nauk, Ser. Khim., 741 (2003).Google Scholar
  10. 10.
    R. A. Gazzaeva, S. S. Mochalov, B. P. Archegov, and N. S. Zefirov, Khim. Geterotsikl. Soedin., 302 (2005). [Chem. Heterocycl. Comp., 41, 272 (2005)].Google Scholar
  11. 11.
    N. Ichinose, K. Mizuno, T. Tamai, and Y. Otsuji, Chem. Lett., 233 (1988).Google Scholar
  12. 12.
    K. Mizuno, N. Ichinose, T. Tamai, and Y. Otsuji, J. Org. Chem., 57, 4669 (1992).CrossRefGoogle Scholar
  13. 13.
    S.-T. Lin, S.-H. Kuo, and F.-M. Yang, J. Org. Chem., 62, 5229 (1997).CrossRefGoogle Scholar
  14. 14.
    A. Z. Kadzhaeva, E. V. Trofimova, R. A. Gazzaeva, A. N. Fedotov, and S. S. Mochalov, Vestn. Moskovsk. Gos. Univ., Ser. 2, Khimiya, 50, 35 (2009).Google Scholar
  15. 15.
    H.-U. Reissig and R. Zimmer, Chem. Rev., 103, 1151 (2003).CrossRefGoogle Scholar
  16. 16.
    M. Yu and B. L. Pagenkopf, Tetrahedron, 61, 321 (2005).CrossRefGoogle Scholar
  17. 17.
    A. M. Bernard, A. Frongia, P. P. Piras, F. Secci, and M. Spiga, Org. Lett., 7, 4565 (2005).CrossRefGoogle Scholar
  18. 18.
    A. M. Bernard, A. Frongia, F. Secci, G. Delogu, J. Ollivier, P. P. Piras, and J. Salaün, Tetrahedron, 59, 9433 (2003).CrossRefGoogle Scholar
  19. 19.
    M. Yu and B. L. Pagenkopf, Org. Lett., 5, 5099 (2003).CrossRefGoogle Scholar
  20. 20.
    J. V. Girvello, J. Org. Chem., 46, 3056 (1981).CrossRefGoogle Scholar
  21. 21.
    M. A. Weidner-Wells, S. A. Fraga-Spano, and I. J. Turchi, J. Org. Chem., 63, 6319 (1998).CrossRefGoogle Scholar
  22. 22.
    S. S. Mochalov, R. A. Gazzaeva, A. N. Fedotov, E. V. Trofimova, I. V. Trushkov, and N. S. Zefirov, Zh. Org. Khim., 40, 1146 (2004).Google Scholar
  23. 23.
    A. Burger and W. L. Yost, J. Am. Chem. Soc., 70, 2198 (1948).CrossRefGoogle Scholar
  24. 24.
    V. Grinshtein and M. Andersone, Izv. Akad. Nauk LatvSSR, Ser. Khim., 106 (1963).Google Scholar
  25. 25.
    A. Nakamura, A. Konishi, R. Tsujitani, M. Kudo, and S. Otsuka, J. Am. Chem. Soc., 100, 3449 (1978).CrossRefGoogle Scholar
  26. 26.
    A. Dupin and R. Fraisse-Jullien, Bull. Soc. Chim. Fr., 1993 (1964).Google Scholar
  27. 27.
    A. N. Fedotov, E. V. Trofimova, S. S. Mochalov, and Yu. S. Shabarov, Zh. Org. Khim., 24, 1413 (1988).Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2009

Authors and Affiliations

  • A. Z. Kadzhaeva
    • 1
  • E. V. Trofimova
    • 2
  • A. N. Fedotov
    • 2
    Email author
  • K. A. Potekhin
    • 2
  • R. A. Gazzaeva
    • 1
  • S. S. Mochalov
    • 2
  • N. S. Zefirov
    • 2
  1. 1.K. L. Hetagurov North-Ossetian State UniversityVladikavkazNorth OssetiaRussia
  2. 2.M. V. Lomonosov Moscow State UniversityMoscowRussia

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