Grunwald-Winstein Relations in the Solvolyses of Highly Congested Simple Secondary and Tertiary Alkyl Systems. Evidence for the Brønsted Base-Type Solvation in the Standard 1- and 2-Adamantyl Systems

Journal of Organic Chemistry

Volumn 62, Issue 15, 1997, Pages 4904-4905

  Takeuchi, Ken'ichi ^a   Ohga, Yasushi ^a   Ushino, Takuhiro ^a   Takasuka, Masaaki ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

PENTANE; PROPANOL; TRIFLUOROETHANOL;

ARTICLE; FLUORINATION; HYDROGEN BOND; IONIZATION; SOLVATION;

EID: 0030807650     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970709x     Document Type: Article

References (28)

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2. Reviews: (a) Bentley, T. W.; Schleyer, P. v. R. Adv. Phys. Org. Chem. 1977, 14, 1. (b) Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121. (c) Kevill, D. N.; D'Souza, M. J. J. Phys. Org. Chem. 1992, 5, 287. (d) Liu, K. T. J. Chinese Chem. Soc. 1995, 42, 607. (e) Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; Vol. 1, pp 81-115.
3. Reviews: (a) Bentley, T. W.; Schleyer, P. v. R. Adv. Phys. Org. Chem. 1977, 14, 1. (b) Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121. (c) Kevill, D. N.; D'Souza, M. J. J. Phys. Org. Chem. 1992, 5, 287. (d) Liu, K. T. J. Chinese Chem. Soc. 1995, 42, 607. (e) Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; Vol. 1, pp 81-115.
4. Reviews: (a) Bentley, T. W.; Schleyer, P. v. R. Adv. Phys. Org. Chem. 1977, 14, 1. (b) Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121. (c) Kevill, D. N.; D'Souza, M. J. J. Phys. Org. Chem. 1992, 5, 287. (d) Liu, K. T. J. Chinese Chem. Soc. 1995, 42, 607. (e) Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; Vol. 1, pp 81-115.
5. Reviews: (a) Bentley, T. W.; Schleyer, P. v. R. Adv. Phys. Org. Chem. 1977, 14, 1. (b) Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121. (c) Kevill, D. N.; D'Souza, M. J. J. Phys. Org. Chem. 1992, 5, 287. (d) Liu, K. T. J. Chinese Chem. Soc. 1995, 42, 607. (e) Kevill, D. N. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, 1996; Vol. 1, pp 81-115.
6. (a) Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667.
7. (b) Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741.
8. Takeuchi, K.; Ohga, Y.; Ushino, T.; Takasuka, M. J. Phys. Org. Chem. 1996, 9, 777.
9. Takeuchi, K.; Ohga, Y.; Ushino, T.; Takasuka, M. J. Phys. Org. Chem., in press.
10. For a recent leading article on Brønsted base-type solvation in solvolytic reactions, see: Richard, J. P.; Jagannadham, V.; Amyes, T. L.; Mishima, M.; Tsuno, Y. J. Am. Chem. Soc. 1994, 116, 6706.
11. Brown, H. C.; Berneis, H. L. J. Am. Chem. Soc. 1953, 75, 10.
12. 5: mp 7-8°C. Spectral and microanalytical data were consistent with the structure. For the precursor alcohol, see: Herberg, C.; Verevkin, S. P.; Nölke, M.; Beckhaus, H.-D.; Rüchardt, C. Liebigs Ann. 1995, 515.
13. Fujio, M.; Saeki, Y.; Nakamoto, K.; Yatsugi, K.; Goto, N.; Kim, S.-H.; Tsuji, Y.; Rappoport, Z.; Tsuno, Y. Bull. Chem. Soc. Jpn. 1995, 68, 2603.
14. 8 Previous values reported by Bentley et al. are compiled in ref 1b.
15. The normal substitution product was formed in 6.2% (in MeOH) and <2% yield (in TFE) from 4 and 2.3% (in MeOH) and 1.3% yield (in TFE) from 5 in the presence of excess 2,6-lutidine at 25°C, the rest being unrearranged olefins.
16. 12c However, we have found that 1-(2-chloro-2-methylpropyl)adamantane that has a bulky 1-adamantyl group in place of the tert-butyl group in 3 and 1-bromo-3,5,7-trimethyladamantane, where cation solvation would be less effective than 1-bromoadamantane, also exhibit upward deviations of TFE or 97% HFIP points. The data will be reported in a full paper.
17. (a) Paradisi, C.; Bunnett, J. F. J. Am. Chem. Soc. 1985, 107, 8223.
18. (b) Stoelting, D. T.; Shiner, V. J., Jr. J. Am. Chem. Soc. 1993, 115, 1695.
19. (c) Kevill, D. N.; Kyong, J. B.; Weitl, F. L. J. Org. Chem. 1990, 55, 4304.
20. (a) Liggero, S. H.; Harper, J. J.; Schleyer, P. v. R.; Krapcho, A. P.; Horn, D. E. J. Am. Chem. Soc. 1970, 92, 3789.
21. (b) Roberts, D. D.; Hall, E. W. J. Org. Chem. 1988, 53, 2573.
22. For leading references, see: (a) Raber, D. J.; Harris, J. M.; Hall, R. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1971, 93, 4821. (b) Sneen, R. A. Acc. Chem. Res. 1973, 6, 46. (c) Raber, D. J.; Harris, J. M.; Schleyer, P. v. R. In Ions and Ion Pairs in Organic Reactions; Szwarc, M., Ed.; Wiley-Interscience: New York, 1974; Vol. 2, pp 247-374.
23. For leading references, see: (a) Raber, D. J.; Harris, J. M.; Hall, R. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1971, 93, 4821. (b) Sneen, R. A. Acc. Chem. Res. 1973, 6, 46. (c) Raber, D. J.; Harris, J. M.; Schleyer, P. v. R. In Ions and Ion Pairs in Organic Reactions; Szwarc, M., Ed.; Wiley-Interscience: New York, 1974; Vol. 2, pp 247-374.
24. For leading references, see: (a) Raber, D. J.; Harris, J. M.; Hall, R. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1971, 93, 4821. (b) Sneen, R. A. Acc. Chem. Res. 1973, 6, 46. (c) Raber, D. J.; Harris, J. M.; Schleyer, P. v. R. In Ions and Ion Pairs in Organic Reactions; Szwarc, M., Ed.; Wiley-Interscience: New York, 1974; Vol. 2, pp 247-374.
25. The b-values were calculated by using the rate data in ref 14a.
26. (a) Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845.
27. (b) Kevill, D. N.; D'Souza, M. J. J. Chem. Res., Synop. 1993, 174.
28. For the rate of tert-butyl chloride in TFE, see: Shiner, V. J., Jr.; Dowd, W.; Fisher, R. D.; Hartshorn, S. R.; Kessick, M. A.; Milakofsky, L.; Rapp, M. W. J. Am. Chem. Soc. 1969, 91, 4838.