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Benzyn-Zwischenprodukte in der nukleophilen aromatischen Substitution

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Summary

Many substitution reactions of aromatic halides, such as amination with metallic amides in ammonia or amine solutions, high-temperature alkaline hydrolyses and arylation with phenyllithium, lead to the formation of rearrangement products as the result of a common reaction path involving unstable ‘benzyne’ intermediates. The chemical evidence in favor of this reaction mechanism is discussed as are correlations of observed product compositions and applications to practical synthetic procedures.

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Literatur

  1. G. Wittig, Angew. Chem.69, 245 (1957).

    Article  CAS  Google Scholar 

  2. F. W. Bergstrom, R. E. Wright, C. Chandler undW. A. Gilkey, J. org. Chem.1, 170 (1936).

    Article  CAS  Google Scholar 

  3. H. Gilman, R. H. Kyle undR. A. Benkeser, J. Amer. chem. Soc.68, 143 (1946).

    Article  CAS  Google Scholar 

  4. H. Gilman undR. H. Kyle, ibid.70, 3945 (1948).

    Article  CAS  Google Scholar 

  5. H. Gilman undS. Avakian, ibid.67, 349 (1945).

    Article  CAS  Google Scholar 

  6. J. D. Roberts, C. W. Vaughan, L. A. Carlsmith undD. A. Semenow, ibid.78, 611 (1956).

    Article  CAS  Google Scholar 

  7. H. Gilman undS. Avakian, ibid.67, 349 (1945).

    Article  CAS  Google Scholar 

  8. J. D. Roberts, C. W. Vaughan, L. A. Carlsmith undD. A. Semenow, J. Amer. chem. Soc.78, 611 (1956).

    Article  CAS  Google Scholar 

  9. H. Gilman undR. H. Kyle, J. Amer. chem. Soc.70, 3945 (1948).

    Article  CAS  Google Scholar 

  10. J. D. Roberts, H. E. Simmons, Jr., L. A. Carlsmith undC. W. Vaughan, ibid.75, 3290 (1953);J. D. Roberts, D. A. Semenow, H. E. Simmons, Jr. undL. A. Carlsmith, ibid.78, 601 (1956).

    Article  CAS  Google Scholar 

  11. F. W. Bergstrom, R. E. Wright, C. Chandler undW. A. Gilkey, J. org. Chem.1, 170 (1936).

    Article  CAS  Google Scholar 

  12. R. E. Wright undF. W. Bergstrom, ibid.1, 179 (1936).

    Article  CAS  Google Scholar 

  13. R. A. Seibert undF. W. Bergstrom, ibid.10, 544 (1945).

    Article  CAS  Google Scholar 

  14. F. W. Bergstrom undR. Agostinho, J. Amer. chem. Soc.67, 2152 (1945).

    Article  CAS  Google Scholar 

  15. P. H. Dirstine undF. W. Bergstrom, J. org. Chem.11, 55 (1946).

    Article  CAS  Google Scholar 

  16. F. Scardiglia undJ. D. Roberts, Tetrahedron (im Druck).

  17. F. Scardiglia undJ. D. Roberts, J. org. Chem.23, 629 (1958).

    Article  CAS  Google Scholar 

  18. J. D. Roberts, A. T. Bottini undD. A. Semenow, Science122, 881 (1955).

    Article  Google Scholar 

  19. A. T. Bottini undJ. D. Roberts, J. Amer. chem. Soc.79, 1458 (1957).

    Article  CAS  Google Scholar 

  20. A. Lüttringhaus undD. Ambros, Ber. dtsch. chem. Ges.89, 463 (1956).

    Article  Google Scholar 

  21. G. Wittig, G. Pieper undG. Fuhrmann, ibid.73, 1193 (1940);G. Wittig, Naturwiss.30, 700 (1942); Angew. Chem.69, 245 (1957).

    Article  Google Scholar 

  22. E. F. Jenny undJ. D. Roberts, Helv. chim. Acta38, 1248 (1955).

    Article  CAS  Google Scholar 

  23. G. Wittig, G. Pieper undG. Fuhrmann, Ber. dtsch. chem. Ges.73, 1193 (1940).

    Article  Google Scholar 

  24. G. Wittig, Naturwiss.30, 700 (1942).

    Article  Google Scholar 

  25. G. Wittig undL. Pohmer, Angew. Chem.67, 348 (1955), Ber. dtsch. chem. Ges.89, 334 (1956).

    Article  CAS  Google Scholar 

  26. Vgl. auchH. Gilman undR. D. Gorsich, J. Amer. chem. Soc.79, 2625 (1957).

    Article  CAS  Google Scholar 

  27. G. Wittig undR. Ludwig, Angew. Chem.68, 40 (1956).

    Article  CAS  Google Scholar 

  28. R. Huisgen undH. Rist, Naturwiss.41, 358 (1954).

    Article  CAS  Google Scholar 

  29. R. Huisgen undJ. Sauer, Angew. Chem.69, 390 (1957).

    Google Scholar 

  30. R. Huisgen undL. Zirngibl, ibid.69, 389 (1957).

    Article  CAS  Google Scholar 

  31. R. Huisgen, J. Sauer undA. Hauser, ibid.69, 267 (1957).

    Article  CAS  Google Scholar 

  32. J. F. Bunnett undT. K. Brotherton, J. Amer. chem. Soc.78, 155, 6265 (1956).

    Article  CAS  Google Scholar 

  33. R. Huisgen undJ. Sauer, Angew. Chem.69, 390 (1957).

    Google Scholar 

  34. J. F. Bunnett undR. E. Zahler, Chem. Rev.49, 273 (1951).

    Article  CAS  Google Scholar 

  35. J. F. Bunnett, Quart. Rev.12, 1 (1958).

    Article  CAS  Google Scholar 

  36. H. Gilman, N. N. Crounse, S. P. Massie, Jr., R. A. Benkeser undS. H. Spatz, J. Amer. chem. Soc.67, 2108 (1945).

    Article  Google Scholar 

  37. J. D. Roberts, D. A. Semenow, H. E. Simmons, Jr. undL.A. Carlsmith, J. Amer. chem. Soc.78, 601 (1956).

    Article  CAS  Google Scholar 

  38. G. E. Hall, R. Piccolini undJ. D. Roberts, J. Amer. chem. Soc.77, 4540 (1955).

    Article  CAS  Google Scholar 

  39. A. T. Bottini undJ. D. Roberts, J. Amer. chem. Soc.79, 1458 (1957).

    Article  CAS  Google Scholar 

  40. W. W. Leake undR. Levine, Chem. & Ind.37, 1160 (1955).

    Google Scholar 

  41. R. Huisgen undH. König, Angew. Chem.69, 268 (1957).

    Article  CAS  Google Scholar 

  42. B. F. Hrutford undJ. F. Bunnett, J. Amer. chem. Soc.80, 2021 (1958).

    Article  Google Scholar 

  43. W. Reppe, Deutsche Patente 550403 und 584840.

  44. W. E. Truce et al., J. Amer. chem. Soc.78, 695, 2743, 2748, 2752 (1956);79, 1770 (1957).

    Article  CAS  Google Scholar 

  45. G. Wittig undH. Witt, Ber. dtsch. chem. Ges.74, 1474 (1941).

    Article  Google Scholar 

  46. G. Wittig undG. Harboth, Ber. dtsch. chem. Ges.77, 306 (1944).

    Article  Google Scholar 

  47. A. E. Favorsky undW. Boshowsky, Liebigs Ann. Chem.390, 122 (1912).

    Article  Google Scholar 

  48. F. Scardiglia undJ. D. Roberts, Tetrahedron1, 343 (1957).

    Article  CAS  Google Scholar 

  49. J. F. Bunnett undT. K. Brotherton, J. org. Chem.23, 904 (1958).

    Article  CAS  Google Scholar 

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Author information

Authors and Affiliations

  1. Pharm.-wiss. Abteilung der CIBA A.-G., Basel

    Erwin F. Jenny

  2. California Institute of Technology, Pasadena 4, California, U.S.A.

    Marjorie C. Caserio & John D. Roberts

Authors
  1. Erwin F. Jenny
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  2. Marjorie C. Caserio
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  3. John D. Roberts
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Contribution No. 2390.

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Jenny, E.F., Caserio, M.C. & Roberts, J.D. Benzyn-Zwischenprodukte in der nukleophilen aromatischen Substitution. Experientia 14, 349–354 (1958). https://doi.org/10.1007/BF02159149

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