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Recent aspects of homolytic aromatic substitutions

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Synthetic and Mechanistic Organic Chemistry

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 62))

Abstract

A common aspect characterizing both the homolytic animation and the substitution of protonated hetero-aromatic bases by nucleophilic free radicals is the presence of a nitrogen atom with a positive charge. This presence determines strong polar effects whether it characterizes the radical (\(R_2 \mathop N\limits_ + H\)) or the aromatic substrate (protonated base). The awareness that the global polar effects result from the polar characteristics of both the radical and the substrate has led to new homolytic aromatic substitutions, characterized by high selectivity and versatility. Thus the homolytic substitution acquires a more significant weight in the field of the aromatic substitutions.

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References

  1. Williams, G. H.: Homolytic Aromatic Substitution. London.: Pergamon Press 1960.

    Google Scholar 

  2. Hey, D. H.: Advances in free radical chemistry (ed. G. H. Williams), Vol. II, p. 47. London: Logos-Academic 1967.

    Google Scholar 

  3. Williams, G. H.: Special publication N. 24, p. 25. London: The Chemical Society 1970.

    Google Scholar 

  4. Perkins, M. J.: Free radicals (ed. J. K. Kochi), Vol. II, p. 231. New York: Wiley and Sons 1973.

    Google Scholar 

  5. Hey, D. H., Orman, S., Williams, G. H.: J. Chem. Soc. 1961, 565.

    Google Scholar 

  6. Dailly, B. N.: Ph. D. Thesis, London 1968.

    Google Scholar 

  7. Hey, D. H., Saunders, F. C., Williams, G. H.: J. Chem. Soc. 1964, 3409.

    Google Scholar 

  8. Dannley, R. L., Gregg, E. C.: J. Am. Chem. Soc. 76, 2997 (1954).

    CAS  Google Scholar 

  9. Morrison, R. T., Cages, J., Samkoff, M., Howe, C. A.: J. Amer. Chem. Soc. 84, 4182 (1962).

    Article  Google Scholar 

  10. Hey, D. H., Stirling, C. J. M., Williams, G. H.: J. Chem. Soc. 1955, 3963.

    Google Scholar 

  11. Elofson, R. M., Godallah, F. F., Schultz, K. F.: J. Org. Chem. 36, 1526 (1971).

    CAS  Google Scholar 

  12. Minisci, F.: Synthesis, 1 (1973).

    Google Scholar 

  13. Minisci, F., Porta, O.: Advances in heterocyclic chemistry (ed. A. R. Katritzky), Vol. 16, p. 123. London: Academic Press 1974.

    Google Scholar 

  14. Minisci, F.: Chim. Ind. (Milan), 49, 705 (1967).

    CAS  Google Scholar 

  15. Wolf, M. E.: Chem. Rev. 63, 55 (1963).

    Google Scholar 

  16. Unpublished results.

    Google Scholar 

  17. Minisci, F., Galli, R., Perchinunno, M.: Org. Prep. Proced. 1, 87 (1969).

    CAS  Google Scholar 

  18. Minisci, F., Galli, R., Cecere, M., Trabucchi, V.: Chim. Ind. (Milan) 48, 1147 (1966).

    CAS  Google Scholar 

  19. Minisci, F., Galli, R., Cecere, M.: Chim. Ind. (Milan) 48, 1324 (1966).

    CAS  Google Scholar 

  20. Minisci, F., Galli, R., Cecere, M., Trabucchi, V.: Chim. Ind. (Milan), 48, 716 (1966).

    CAS  Google Scholar 

  21. Minisci, F., Cecere, M.: Chim. Ind. (Milan) 49, 1333 (1967).

    CAS  Google Scholar 

  22. Minisci, F., Trabucchi, V., Galli, R., Bernardi, R.: Chim. Ind. (Milan) 48, 845 (1966).

    CAS  Google Scholar 

  23. Minisci, F., Bernardi, R., Crippa, L., Trabucchi, V.: Chim. Ind. (Milan) 48, 264 (1966).

    CAS  Google Scholar 

  24. Minisci, F., Galli, R., Bernardi, R.: Chim. Ind. (Milan), 49, 252 (1967).

    CAS  Google Scholar 

  25. Minisci, F., Galli, R.: Tetrahedron Lett. 2532 (1966).

    Google Scholar 

  26. Minisci, F., Galli, R., Perchinunno, M.: Org. Prep. Proced. 1, 77 (1969).

    CAS  Google Scholar 

  27. Minisci, F., Malatesta, V.: Chim. Ind. (Milan) 53, 1154 (1971).

    Google Scholar 

  28. Minisci, F., Galli, R., Cecere, M.: Chim. Ind. (Milan), 48, 725 (1966).

    CAS  Google Scholar 

  29. Minisci, F., Galli, R.: Tetrahedron Lett. 433, 4463 (1965).

    Google Scholar 

  30. Minisci, F., Bernardi, R., Trabucchi, V., Crippa, L.: Chim. Ind. (Milan) 48, 484 (1966).

    CAS  Google Scholar 

  31. Clerici, A., Minisci, F., Perchinunno, M., Porta, O.: J. G. S. Perkin II 416 (1974).

    Google Scholar 

  32. Minisci, F., Galli, R.: Chim. Ind. (Milan) 46, 546 (1964).

    CAS  Google Scholar 

  33. Kovacic, P., Lowery, M. L., Field, K. W.: Chem. Rev. 70, 639 (1970).

    Article  CAS  Google Scholar 

  34. Bernardi, R., Galli, R., Minisci, F.: J. Chem. Soc. B 324 (1968).

    Google Scholar 

  35. Minisci, F., Galli, R., Perchinunno, M., Bernardi, R.: Chim. Ind. (Milan) 50, 453 (1968).

    CAS  Google Scholar 

  36. Exner, O.: Advances in linear free energy relationships (eds. N. B. Chapman and J. Sharter), London: Plenum Press 1972.

    Google Scholar 

  37. Katritzky, A. R., Ridgewell, B. J.: J. Chem. Soc. 3753 (1963).

    Google Scholar 

  38. Jaffé, H. H.: J. Amer. Chem. Soc. 77, 4445 (1955).

    Google Scholar 

  39. Jaffé, H. H.: J. Chem. Phys. 20, 1554 (1952).

    Google Scholar 

  40. Minisci, F., Bernardi, R., Bertini, F., Galli, R., Perchinunno, M.: Tetrahedron Lett., 27, 3575 (1971).

    CAS  Google Scholar 

  41. Bertini, F., Caronna, T., Galli, R., Minisci, F., Porta, O.: Chim. Ind. (Milan) 54, 425 (1972).

    CAS  Google Scholar 

  42. Minisci, F., Citterio, A., Perchinunno, M., Bertini, F.: Gazz. Chim. Ital.: in press.

    Google Scholar 

  43. Minisci, F., Galli, R., Malatesta, V., Caronna, T.: Tetrahedron Lett. 26, 4083 (1970).

    CAS  Google Scholar 

  44. Clerici, A., Minisci, F., Porta, O.: Tetrahedron Lett. 29, 2775 (1973).

    CAS  Google Scholar 

  45. Bertini, F., Galli, R., Minisci, F., Porta, O.: Chim. Ind. (Milan) 54, 223 (1972).

    CAS  Google Scholar 

  46. Caronna, T., Filini, L.: Org. Prep. Proced. Int. 105 (1973).

    Google Scholar 

  47. Bertini, F., Caronna, T., Cecere, M.: Org. Prep. Proced. Int. 109 (1973).

    Google Scholar 

  48. Caronna, T., Gardini, G. P., Minisci, F.: Chem. Commun. 201 (1969).

    Google Scholar 

  49. Caronna, T., Fronza, G., Minisci, F., Porta, O.: J. C. S. Perkin II 2035 (1972).

    Google Scholar 

  50. Gardini, G. P., Minisci, F.: J. Chem. Soc. C 929 (1970).

    Google Scholar 

  51. Caronna, T., Galli, R., Malatesta, V., Minisci, F.: J. Chem. Soc. C, 1747 (1971).

    Google Scholar 

  52. Beckwith, A. L. J., Leydon, R. J.: Austral. J. Chem. 21, 817 (1968).

    CAS  Google Scholar 

  53. Bertini, F., Caronna, T., Grossi, L., Minisci, F.: Gazz. Chim. Ital. 104, 471 (1974).

    CAS  Google Scholar 

  54. Ohno, A., Ohuishi, Y.: Tetrahedron Lett. 4405 (1968).

    Google Scholar 

  55. Timnrtlake, J. W., Hodges, M. L.: Tetrahedron Lett. 1970, 4147.

    Google Scholar 

  56. Buratti, W., Gardini, G. P., Minisci, F., Bertini, F., Galli, R., Perchinunno, M.: Tetrahedron Lett. 27, 3655 (1971).

    CAS  Google Scholar 

  57. Ledwith, A., Russel, P. J., Sutchiffe, L. H.: Chem. Commun. 970 (1971).

    Google Scholar 

  58. Kochi, J. K.: Free radicals (ed. J. K. Kochi), Vol. II, p. 670. New York: Wiley and Sons 1973.

    Google Scholar 

  59. Gardini, G. P.: Tetrahedron Lett. 1972, 4113.

    Google Scholar 

  60. Minisci, F., Gardini, G. P., Galli, R., Bertini, F.: Tetrahedron Lett., 1970, 15.

    Google Scholar 

  61. Arnone, A., Cecere, M., Galli, R., Minisci, F., Perchinunno, M., Porta, O., Gardini, G. P.: Gazz. Chim. Ital. 103, 13 (1973).

    CAS  Google Scholar 

  62. Gardini, G. P., Minisci, F., Palla, G., Arnone, A., Galli, R.: Tetrahedron Lett. 1971, 59.

    Google Scholar 

  63. Bernardi, R., Caronna, T., Galli, R., Minisci, F., Perchinunno, M.: Tetrahedron Lett. 1973 645.

    Google Scholar 

  64. Minisci, F., Mondelli, R., Gardini, G. P., Porta, O.: Tetrahedron Lett. 28, 2403 (1972).

    CAS  Google Scholar 

  65. Liveris, M., Miller, J.: J. Chem. Soc. 1963, 3486.

    Google Scholar 

  66. Clerici, A., Minisci, F., Porta, O.: Tetrahedron Lett. 30, 4201 (1974).

    CAS  Google Scholar 

  67. Belli, M. L., Illuminati, G., Marino, G.: Tetrahedron Lett. 19, 345 (1963).

    CAS  Google Scholar 

  68. Greizerstein, W., Bonelli, R. A., Brieux, J. A.: J. Amer. Chem. Soc. 84, 1026 (1962).

    CAS  Google Scholar 

  69. Huang, R. L., Goh, S. H., Ong, S. H.: The chemistry of free radicals, p. 103. London: Arnold 1974.

    Google Scholar 

  70. Shelton, J. R., Uzelmeir, C. W.: J. Amer. Chem. Soc. 88, 5222 (1966).

    Article  CAS  Google Scholar 

  71. Shono, T., Nishiguchi, I.: Tetrahedron Lett. 30, 2183 (1974).

    CAS  Google Scholar 

  72. Clerici, A., Minisci, F., Porta, O.: Gazz. Chim. Ital. 103, 171 (1973).

    CAS  Google Scholar 

  73. Clerici, A., Minisci, F., Porta, O.: J. C. S. Perkin II, 1699 (1974).

    Google Scholar 

  74. Benson, S. W.: J. Chem. Ed. 42, 502 (1965).

    CAS  Google Scholar 

  75. Jones, S. H., Whittle, E.: Intl. J. Chem. Kinetics, 2, 479 (1970).

    CAS  Google Scholar 

  76. Zavitsas, A. A., Pinto, J. A.: J. Amer. Chem. Soc. 94, 7390 (1972).

    CAS  Google Scholar 

  77. Solly, R. K., Benson, S. W.: J. Amer. Chem. Soc. 93, 1592 (1971).

    CAS  Google Scholar 

  78. Alfossi, Z. B., Golden, D. M.: J. Amer. Chem. Soc. 95, 319 (1973).

    Google Scholar 

  79. Dixon, W. T., Norman, R. O. C.: J. Chem. Soc. 1964, 4857.

    Google Scholar 

  80. Krusic, P. J., Rettig, T. A.: J. Amer. Chem. Soc. 92, 722 (1970).

    CAS  Google Scholar 

  81. Caronna, T., Fronza, G., Minisci, F., Porta, O.: J. C. S. Perkin II, 1477 (1972).

    Google Scholar 

  82. Fessenden, R. W., Schuler, R. H.: J. Chem. Phys. 39, 2147 (1963).

    Article  CAS  Google Scholar 

  83. Dewar, M. J. S., Harris, J. M.: J. Amer. Chem. Soc. 91, 3652 (1969).

    CAS  Google Scholar 

  84. Altman, L. J., Vederas, J. C.: Chem. Comm. 1969, 895.

    Google Scholar 

  85. Altman, L. J., Nelson, B. W.: J. Amer. Chem. Soc. 91, 5163 (1969).

    Article  CAS  Google Scholar 

  86. Jacobus, J., Pensak, D.: Chem. Comm. 1969, 400.

    Google Scholar 

  87. Tiecco, M.: personal communication.

    Google Scholar 

  88. Kosower, E. M.: Progress in Phys. Org. Chem. 32, 1 (1967).

    Google Scholar 

  89. Porta, O.: Chim. Ind. (Milan) 56, 693 (1974).

    CAS  Google Scholar 

  90. Vittimberga, B., Minisci, F., Morrocchi, S.: J. Am. Chem. Soc. 97, 4397 (1975).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Istituto di Chimica del Politecnico, Milano, Italy

    Prof. Francesco Minisci

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  1. Prof. Francesco Minisci
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F. Minisci J. B. Hendrickson C. Wentrup

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Minisci, F. (1976). Recent aspects of homolytic aromatic substitutions. In: Minisci, F., Hendrickson, J.B., Wentrup, C. (eds) Synthetic and Mechanistic Organic Chemistry. Topics in Current Chemistry, vol 62. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0046046

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  • DOI: https://doi.org/10.1007/BFb0046046

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