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Effect of substituents in the ring on the structure and electron density distribution in benzyl halides

  • Physical Chemistry
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Russian Chemical Bulletin Aims and scope

Abstract

The results of calculations for benzyl chlorides and benzyl bromides that contain substituents in the ring by different quantum-chemical methods are compared. The electron density on the benzyl carbon atom increases as the electron-withdrawing properties of substituents are enhanced due to the shift of the electron density from the benzyl halogen atom to the adjacent carbon atom. A topological analysis according to Bader confirmed the main reason for the change in the paramagnetic shielding of the benzyl13C nuclei. The results of calculations provide, for the first time, an explanation for the resonance upfield13C shift of this atom as the Hammett constant of a substituent increases in compounds of the series under consideration.

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References

  1. C. K. Ingold,Structure and Mechanism in Organic Chemistry, Cornell University Press, Ithaca, 1969.

    Google Scholar 

  2. J. March,Advanced Organic Chemistry. Reactions Mechanisms and Structure, 3d ed., Wiley, New York, 1985.

    Google Scholar 

  3. K. B. Wiberg and C. M. Breneman,J. Am. Chem. Soc., 1990,112, 8765.

    Article  CAS  Google Scholar 

  4. K. B. Wiberg,J. Org. Chem., 1991,56, 544.

    Article  CAS  Google Scholar 

  5. K. B. Wiberg and K. E. Laidig,J. Org. Chem., 1992,57, 5092.

    Article  CAS  Google Scholar 

  6. Y.-D. Wu, C.-L. Wong, K. W. K Chan, G.-Z. Ji, and X.-K. Jiang,J. Org. Chem., 1996,61, 746.

    Article  CAS  Google Scholar 

  7. S. S> Shaik,Progr. Phys. Org. Chem., 1985,15, 197.

    CAS  Google Scholar 

  8. G. A. Russel,Adv. Phys. Org. Chem., 1987,23, 271.

    Google Scholar 

  9. I. Lee,Adv. Phys. Org. Chem., 1992,27, 57.

    CAS  Google Scholar 

  10. R. Ta-Shma and Z. Rappoport,Adv. Phys. Org. Chem., 1992,27, 239.

    CAS  Google Scholar 

  11. S. Chang, H. J. Koh, B.-S. Lee, and I. Lee,J. Org. Chem., 1995,60, 7760.

    Article  CAS  Google Scholar 

  12. P. I. Dem'yanov, G. V. Fedorova, V. S. Petrosyan, and O. A. Reutov,Metalloorg. Khim., 1989,2, 620 [Organomet. Chem. USSR, 1989,2 (Engl. Transl.)].

    Google Scholar 

  13. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, and J. A. Montgomery, Jr.,J. Comput. Chem., 1993,14, 1347.

    Article  CAS  Google Scholar 

  14. M. J. S. Dewar and W. Thiel,J. Am. Chem. Soc., 1977,99, 4899.

    Article  CAS  Google Scholar 

  15. M. J. S. Dewar and W. Thiel,J. Am. Chem. Soc., 1977,99, 4907.

    Article  CAS  Google Scholar 

  16. J. J. P. Stewart,J. Comput. Chem., 1989,10, 209.

    Article  CAS  Google Scholar 

  17. J. J. P. Stewart,QCPE Bull., Program No. 455.

  18. R. F. W. Bader,Atoms in Molecules. A Quantum Theory, Clarendon Press, Oxford, 1994, 438 pp.

    Google Scholar 

  19. V. G. Tsirel'son,Itogi nauki i tekhniki. Kristallokhimiya, [Results of Science and Engineering. Crystal Chemistry], VINITI, Moscow, 1993,27, 3 (in Russian).

    Google Scholar 

  20. F. W. Biegler-König, R. F. W. Bader, and T.-H. Tang,J. Comput. Chem., 1982,3, 317.

    Article  Google Scholar 

  21. C. Hansch, A. Leo, and R. W. Taft,Chem. Rev., 1991,91, 165.

    Article  CAS  Google Scholar 

  22. J. M. Hollas, J. J. C. Teixeira-Dias, and P. J. A. Ribeiro-Claro,Chem. Phys. Lett., 1989,157, 31.

    Article  Google Scholar 

  23. M. I. Sadova, L. V. Vilkov, I. Hargittai, and J. Brunvoll,J. Mol. Struct., 1976,31, 131.

    Article  CAS  Google Scholar 

  24. S. J. Ashcroft, A. S. Carson, and J. B. Pedley,Trans. Faraday Soc., 1963,59, 2713.

    Article  CAS  Google Scholar 

  25. J. J. P. Stewart,J. Comput. Chem., 1989,10, 221.

    Article  CAS  Google Scholar 

  26. T. Schaefer, R. Sebastian, and G. H Penner,Can. J. Chem., 1986,64, 1372.

    CAS  Google Scholar 

  27. G. H. Penner, T. Schaefer, R. Sebastian, and S. Wolfe,Can. J. Chem., 1987,65, 1845.

    Article  CAS  Google Scholar 

  28. V. P. Feshin and M. Yu. Kon'shin,Izv. Akad. Nauk, Ser. Khim., 1996, 823 [Russ. Chem. Bull., 1996,45, 777 (Engl. Transl.)].

    Google Scholar 

  29. W. Hummel, K. Huml, and H.-B. Bürgi,Helv. Chem. Acta, 1988,71, 1291.

    Article  CAS  Google Scholar 

  30. S. Irle, T. M. Krygowski, J. E. Niu, and W. H. E. Schwarz,J. Org. Chem., 1995,60, 6744.

    Article  CAS  Google Scholar 

  31. A Pross and L. Radom,Progr. Phys. Org. Chem., 1981,13, 1.

    CAS  Google Scholar 

  32. R. S. Mulliken,J. Chem. Phys., 1955,23, 1833.

    Article  CAS  Google Scholar 

  33. A. E. Reed, I. A. Curtiss, and F. Weihold.,Chem. Rev., 1988,88, 899.

    Article  CAS  Google Scholar 

  34. Electronegativity, Eds. K. D. Sen and C. K. Jørgensen, Springer-Verlag, Berlin, 1987, 198 pp.

    Google Scholar 

  35. W. J. Hehre, L. Radom, P. v. R. Schleyer, and J. A. Pople,Ab initio Molecular Orbital Theory, Wiley, New York, 1986, 548 pp.

    Google Scholar 

  36. J. Cioslowski,J. Am. Chem. Soc., 1989,111, 8333.

    Article  CAS  Google Scholar 

  37. A. Streitwieser, S. M. Bachrach, A. Dorigo, and P. v. R. Schleyer, inLithium Chemistry. A Theoretical and Experimental Overview, Eds. A.-M. Sapse and P. v. R. Schleyer, Wiley, New York, 1995, 1.

    Google Scholar 

  38. K. B. Wiberg and P. R. Rablen,J. Comput. Chem., 1993,14, 1504.

    Article  CAS  Google Scholar 

  39. T. S. Slee,J. Am. Chem. Soc., 1986,108, 7541.

    Article  CAS  Google Scholar 

  40. K. B. Wiberg and M. A. Murcko,J. Phys. Chem., 1987,91, 3616.

    Article  CAS  Google Scholar 

  41. B. S. Stefanov and J. Cioslowski,J. Comput. Chem., 1995,16, 1394.

    Article  CAS  Google Scholar 

  42. M. Charton,Progr. Phys. Org. Chem., 1971,8, 235.

    CAS  Google Scholar 

  43. D. J. Craik and R. T. C. Brownlee,Progr. Phys. Org. Chem., 1983,14, 1.

    CAS  Google Scholar 

  44. J. Bromilow, R. T. C. Brownlee, and D. J. Craik,Aust. J. Chem., 1977,30, 351.

    Article  CAS  Google Scholar 

  45. D. G. Farnum,Adv. Phys. Org. Chem., 1975,11, 123.

    CAS  Google Scholar 

  46. J. B. Grutzner, inRecent Advances in Organic NMR Spectroscopy, Eds. J. B. Lambert and R. Rittner, Norell Press, Landisville, 1987, 17.

    Google Scholar 

  47. M. Kubota and S. Ohba,Acta Cryst., 1992,B48, 849.

    Article  Google Scholar 

  48. M. Tonogaki, T. Kawata, and S. Ohba,Acta Cryst., 1993,B49, 1031.

    Article  Google Scholar 

  49. J. Raber, J. M. Harris, and P. v. R. Schleyer, inIon and Ion Pairs in Organic Reactions, Ed. M. Szwarc, Wiley, New York, 1974,2, 247.

    Google Scholar 

  50. Structure and Bonding, Ed. K. D. Sen, Springer-Verlag, Berlin, 1993, 80.

    Google Scholar 

  51. O. A. Reutov, I. P. Beletskaya, and A. L. Kurz,Ambident Anions, Consultants Bureau, New York, 1983, 338 pp.

    Google Scholar 

  52. D. D. Tanner, J. A. Plambeck, D. W. Reed, and T. W. Mojelsky,J. Org. Chem., 1980,45, 5177.

    Article  CAS  Google Scholar 

  53. X.-M. Zhang,J. Chem. Soc., Perkin Trans. 2, 1993, 2275.

  54. N. Kornblum,Angew. Chem. Int. Ed. Engl., 1975,14, 734.

    Article  Google Scholar 

  55. J.-M. Sav éant,Adv. Phys. Org. Chem., 1990,26, 1.

    Article  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, Vorob'evy Gory, 119899, Moscow, Russian Federation

    P. I. Dem'yanov, E. M. Myshakin, D. P. Krut'ko & V. S. Petrosyan

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  1. P. I. Dem'yanov
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  2. E. M. Myshakin
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  3. D. P. Krut'ko
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  4. V. S. Petrosyan
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2111–2119, December, 1997.

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Dem'yanov, P.I., Myshakin, E.M., Krut'ko, D.P. et al. Effect of substituents in the ring on the structure and electron density distribution in benzyl halides. Russ Chem Bull 46, 1996–2005 (1997). https://doi.org/10.1007/BF02495241

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  • DOI: https://doi.org/10.1007/BF02495241

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