Skip to main content
SpringerLink
Log in

Reactivities and structures of compounds of the thiophene and furan series bearing electron-acceptor substituents

  • Published:
Chemistry of Heterocyclic Compounds Aims and scope

Abstract

The experimental data on orientation in electrophilic substitution reactions of compounds of the furan and thiophene series that bear electron-acceptor substituents were examined. Within the framework of the CNDO/2 method, the electronic structures, dipole moments, and spin-spin coupling constants in the PMR spectra were calculated for model systems — 2-formylthiophene, furfural, and their oxygen-protonated forms. The results of the calculations are compared with the available experimental data on the dipole moments and spin-spin coupling constants, which made it possible to discuss the geometrical structures of the compounds. An analysis of data on the chemical behavior of these compounds demonstrated that, in contrast to the charges found using the π-electron approximation, the total charges on the atoms calculated by the CNDO/2 method are rather effective indexes of the reactivity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Literature cited

  1. M. E. Vol'pin, Usp. Khim., 29, 298 (1960).

    Google Scholar 

  2. G. Marino, Tetrahedron, 21, 843 (1965).

    Google Scholar 

  3. S. Clementi, P. Linda, and G. Marino, Tetrah. Lett., 1389 (1970).

  4. A. R. Butler and J. R. Hendry, J. Chem. Soc., B, 170 (1970).

  5. A. I. Shatenshtein, A. G. Kamrad, I. O. Shapiro, Yu. I. Ranneva, and E. N. Zvyagintseva, Dokl. Akad. Nauk SSSR, 166, 364 (1966).

    Google Scholar 

  6. S. Clementi, P. Linda, and G. Marino, J. Chem. Soc., B, 1153 (1970).

  7. R. Taylor, J. Chem. Soc., B, 1397 (1968).

  8. R. Taylor, J. Chem. Soc., B, 1364 (1970).

  9. F. B. Deans and C. Eaborn, J. Chem. Soc., 2303 (1959).

  10. H. Gilman and G. F. Wright, Chem. Rev., 11, 323 (1932).

    Google Scholar 

  11. Ya. L. Gol'dfarb (Ja. L. Goldfarb), Yu. B. Vol'kenshtein (Ju. B. Volkenstein),and L. I. Belen'kii (L. E. Belenkij), Angew. Chem., 80, 547 (1968).

    Google Scholar 

  12. Ya. L. Gol'dfarb and L. D. Krasnoslobodskaya, Usp. Khim., 38, 854 (1969).

    Google Scholar 

  13. Ya. L. Gol'dfarb, A. P. Yakubov, and L. I. Belen'kii, Dokl. Akad. Nauk SSSR, 185, 94 (1969).

    Google Scholar 

  14. L. I. Belen'kii, G. P. Gromova, and Ya. L. Gol'dfarb, Izv. Akad. Nauk SSSR, Ser. Khim., 1228 (1971).

  15. L. I. Belen'kii, I. B. Karmanova, Yu. B. Vol'kenshtein, and Ya, L. Gol'dfarb, Izv. Akad. Nauk SSSR, Ser. Khim., 956 (1971).

  16. L. I. Belen'kii, I. B. Karmanova, and Ya. L. Gol'dfarb, Zh. Organ. Khim., 7, 1743 (1971).

    Google Scholar 

  17. L. I. Belen'kii, É. I. Novikova, and Ya. L. Gol'dfarb, Fourth Symposium on Organic Sulphur, Abstracts of Papers, Venice, 31 (1970).

  18. Ya. L. Gol'dfarb, É. I. Novikova, and L. E. Belen'kii, Izv. Akad. Nauk SSSR, Ser. Khim., 1233 (1971).

  19. L. I. Belen'kii, É. I. Novikova, I. A. D'yachenko, and Ya. L. Gol'dfarb, Zh. Organ. Khim., 7, 1736, (1971).

    Google Scholar 

  20. Ya. L. Gol'dfarb, É. I. Novikova, and L. I. Belen'kii, Izv. Akad. Nauk SSSR, Ser. Khim., 2841 (1971).

  21. L. I. Belen'kii, É. I. Novikova, and Ya. L. Gol'dfarb, Khim. Geterotsikl. Soedin., 1353 (1971).

  22. L. A. Boiko and Yu. A. Boiko, Khim. Geterotsikl. Soedin., 1135 (1969).

  23. H. Gilman, M. McCorkle, and N. O. Callaway, J. Am. Chem. Soc., 56, 745 (1934).

    Google Scholar 

  24. H. Gilman and R. R. Burton, J. Am. Chem. Soc., 57, 909 (1935).

    Google Scholar 

  25. K. K. Venters and S. A. Gillers, Nitro Compounds (Proceedings of the International Symposium), Warsaw, 71 (1964).

  26. E. A. Kehrer and E. Hofacker, Ann., 294, 165 (1897).

    Google Scholar 

  27. M. Szakacs-Pinte and L. Maros, Acta China. Acad. Hung., 56, 199 (1968).

    Google Scholar 

  28. N. Elming, in: Advances in Organic Chemistry [Russian translation], Vol. 2, Mir, Moscow (1954), p. 62.

    Google Scholar 

  29. J. A. Pople and G. A. Segal, J. Chem. Phys., 44, 3289 (1966).

    Google Scholar 

  30. Program No. 141, Quantum Chemistry Program Exchange, Indiana Univ., USA.

  31. J. A. Pople and M. Gordon, J. Am. Chem. Soc., 89, 4253 (1967).

    Google Scholar 

  32. D. P. Santry and G. A. Segal, J. Chem. Phys., 47, 158 (1967).

    Google Scholar 

  33. D. P. Santry, J. Am. Chem. Soc., 90, 3309 (1968).

    Google Scholar 

  34. J. A. Pople and D. P. Santry, Mol. Phys., 8, 1 (1964).

    Google Scholar 

  35. N. D. Chuvylkin and G. M. Zhidomirov, Zh. Strukt. Khim., 12, 347 (1971).

    Google Scholar 

  36. R. B. Hermann, J. Am. Chem. Soc., 91, 3152 (1969).

    Google Scholar 

  37. R. B. Hermann, Intern. J. Quant. Chem., 2, 165 (1968).

    Google Scholar 

  38. T. R. Lewis, Tetrahedron, 25, 4117 (1969).

    Google Scholar 

  39. A. Streitwieser, H. A. Hammond, R. H. Jagow, R. M. Williams, R. C. Jesaitis, C. J. Change, and R. Wolf, J. Am. Chem. Soc., 92, 5141 (1970).

    Google Scholar 

  40. R. B. Hermann, J. Am. Chem. Soc., 92, 5298 (1970).

    Google Scholar 

  41. R. D. Bach and H. F. Henneike, J. Am. Chem. Soc., 92, 5589 (1970).

    Google Scholar 

  42. R. W. Atkin and T. A. Claxton, Trans. Faraday Soc., 66, 257 (1970).

    Google Scholar 

  43. D. T. Clark, Tetrahedron, 24, 3285 (1968).

    Google Scholar 

  44. D. T. Clark, Tetrahedron, 24, 2663 (1968).

    Google Scholar 

  45. B. Bak, D. Christensen, W. Dixon, L. Hansen-Nygaard, J. Rastrup-Andersen, and M. Schottlander, J. Mol. Spectr., 9, 124 (1962).

    Google Scholar 

  46. B. Bak, D. Christensen, L. Hansen-Nygaard, and J. Rastrup-Andersen, J. Mol. Spectr., 7, 58 (1961).

    Google Scholar 

  47. K. H. Kovalenko, V. I. Minkin, Z. N. Nazarova, and D. V. Kazachenko, Zh. Obshch. Khim., 32, 549 (1962).

    Google Scholar 

  48. S. Gronowitz, G. Sörlin, B. Gestblom, and R. A. Hoffmann, Arkiv Kemi, 19, 483 (1963).

    Google Scholar 

  49. H. Lumbroso and P. Pastour, Comptes. Rend., 261, 1279 (1965).

    Google Scholar 

  50. R. A. Hoffmann and S. Gronowitz, Arkiv Kemi, 16, 515 (1960).

    Google Scholar 

  51. K. I. Dalqvist and S. Forsen, J. Phys. Chem., 69, 1760 (1965).

    Google Scholar 

  52. B. Roques, S. Combrisson, C. Riche, and C. Pascard-Dilly, Tetrahedron, 26, 3555 (1970).

    Google Scholar 

  53. M. L. Martin, J.-C. Roze, C. J. Martin, and P. Fournari, Tetrah. Lett., 1720 (1970).

  54. H. Lumbroso, D. M. Bertin, and P. Cagniant, Bull. Soc. Chim. France, 1720 (1970).

  55. L. Kaper and T. J. de Boer, Rec. Trav. Chim., 89, 825 (1970).

    Google Scholar 

  56. H. J. Strenzman and H. Schenk, Rec. Trav. Chim., 89, 392 (1970).

    Google Scholar 

  57. C. McLean, J. H. van der Waals, and E. L. Mackor, Mol. Phys., 1, 247 (1958).

    Google Scholar 

  58. C. McLean and E. L. Mackor, J. Chem. Phys., 34, 2207 (1961).

    Google Scholar 

  59. D. M. Brouwer, Rec. Trav. Chim., 86, 879 (1967).

    Google Scholar 

  60. M. Brockhart, G. C. Levy, and S. Winstein, J. Am. Chem. Soc., 89, 1735 (1967).

    Google Scholar 

  61. H. Hogeveen, Rec. Trav. Chim., 86, 696, 809 (1967).

    Google Scholar 

  62. I. Linquist, Inorganic Adduct Molecules of Oxo-Compounds, Berlin, (1963), p. 95.

  63. W. Gerrard, M. F. Lappert, H. Pyssora, and J. W. Wallis, J. Chem. Soc., 2144 (1960).

  64. U. Henriksson and S. Forsen, Chem. Commun., 1229 (1970).

  65. K. F. Purcell and J. M. Collins, J. Am. Chem. Soc., 92, 465 (1970).

    Google Scholar 

  66. P. Ros, J. Chem. Phys., 49, 4902 (1968).

    Google Scholar 

  67. A. Streitwieser, Molecular Orbital Theory for Organic Chemists, Wiley (1961).

  68. V. S. Bogdanov, M. A. Kalik, G. M. Zhidomirov, N. D. Chuvylkin, and Ya. L. Gol'dfarb, Zh. Organ. Khim., 7, 1953 (1971).

    Google Scholar 

  69. Ya. L. Gol'dfarb, S. Z. Taits, T. S. Chirkova, and L. I. Belen'kii, Izv. Akad. Nauk SSSR, Ser. Khim., 2055 (1964).

  70. J. Skramstad, Acta Chem. Scand., 22, 2445 (1968).

    Google Scholar 

  71. S. Suny, O. Chalvet, and R. Daudel, J. Chim. Phys., 57, 31 (1960).

    Google Scholar 

  72. S. A. Shevelev, Usp. Khim., 39, 1773 (1970).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow

    Ya. L. Gol'dfarb, G. M. Zhidomirov, N. D. Chuvylkin & L. I. Belen'kii

Authors
  1. Ya. L. Gol'dfarb
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. G. M. Zhidomirov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. N. D. Chuvylkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. L. I. Belen'kii
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 155–164, February, 1972.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Gol'dfarb, Y.L., Zhidomirov, G.M., Chuvylkin, N.D. et al. Reactivities and structures of compounds of the thiophene and furan series bearing electron-acceptor substituents. Chem Heterocycl Compd 8, 136–143 (1972). https://doi.org/10.1007/BF00472342

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00472342

Keywords

Search

Navigation