A Dramatic Solvent Effect during Aromatic Halogen—Metal Exchanges. Different Products from Lithiation of Polyfluorobromobenzenes in Ether and THF

Journal of Organic Chemistry

Volumn 55, Issue 2, 1990, Pages 773-775

  Patt, William C ^a   Stickney, Thomas M ^a   Bridges, Alexander J ^b  

^a PFIZER INC   (United States)

^b EISAI RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0011818899     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00289a069     Document Type: Article

References (30)

1. Belf, L. J.; Buxton, M. W.; Tilney-Bussett, J. F. Tetrahedron 1967, 23, 4719.
2. Parham, W. E.; Jones, L. D.; Sayed, Y. A. J. Org. Chem. 1976, 41, 1184.
3. Parham, W. E.; Jones, L. D. J. Org. Chem. 1976, 41, 1187, 2704.
4. Seebach, D.: Neumann, H. Chem. Ber. 1974. 107. 847.
5. For numerous examples, see: Wakefield, B. J. The Chemistry of Organolithium Compounds; Pergamon Press: Oxford, 1974; Chapters 3 and 4.
6. Gschwend, H. W.; Rodriguez, H. R. Org. React. 1979, 26, 1.
7. Gilman, H.; Langham, W.; Jacoby, A. L. J. Am. Chem. Soc. 1939, 61, 106.
8. Gilman, H.; Langham, W.; Willis, H. B. J. Am. Chem. Soc. 1940, 62, 346.
9. Gilman, H.; Laneham, W.: Moore, F. W. J. Am. Chem. Soc. 1940. 62. 2327.
10. Bridges, A. J.; Domagala, J. M. U.S. Patent 4,803,205, 1989.
11. Upton, C. J.; Beak, P. J. Org. Chem. 1975, 40, 1094.
12. Krizan, T. D.; Martin, J. C. J. Am. Chem. Soc. 1983, 105, 6155.
13. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 105, 7909.
14. Beak, P.; Snieckus, V. Acc. Chem. Res. 1982,15, 306.
15. Snieckus, V. Lect. Heterocycl. Chem. Supplement. J. Heterocycl. Chem. 1984, 22, 95.
16. Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356.
17. Taguchi, H.; Yamamoto, H.; Nozaki, H. J. Am. Chem. Soc. 1974, 96, 3010, 6510.
18. Corey, E. J.; Beames, D. J. Am. Chem. Soc. 1972, 94, 7210.
19. See: Cohen, S. C.; Massey, A. G. In Advances in Fluorine Chemistry, Vol. 6; Tatlow, J. C., Peacock, R. D., Hyman, H. H., Eds.; Butterworth: London, 1966; pp 83–105.
20. PhLi is a tetramer in ether. See: Hope, H.; Power, P. P. J. Am. Chem. Soc. 1983, 105, 5320.
21. In the presence of TMEDA it is a dimer. See: Thoennes, D.; Weiss, F. Chem. Ber. 1978, 111, 3157.
22. Fraenkel, G.; Hsu, H.; Su, B. M. Presented at the ACS S,E. Regional Meeting, Charlotte, NC, Nov 1983.
23. In THF it is also a dimer. See: Jackman, L. M.; Scarmoutzos, L. M. J. Am. Chem. Soc. 1984, 106, 4627.
24. Eberhardt, G. G.; Butte, W. A. J. Org. Chem. 1964, 29, 2928.
25. Gjos, N.; Gronowitz, S. Acta Chem. Scand. 1971. 25. 2596.
26. Dickinson, R. P.; Iddon, B. J. Chem. Soc. C 1971, 3447.
27. Mallet, M.; Queguiner, G. Tetrahedron 1979, 35, 1625; 1982, 38, 3035; 1985, 41, 3433; 1986, 42. 2253.
28. Bunnett, J. F. Acc. Chem. Res. 1972, 5, 139.
29. Abe, I.; Kuramoto, S.; Musha, S. J. High Res. Chrom. Commun. 1983, 6, 366.
30. A referee has suggested that some rearrangements may have occurred during catheter transfer, or on warming up prior to acid quench. The high yields of acids from l-bromo-2-lithio compounds and kinetic lithiations suggest that catheter transfer is not problematic. Several of the reactions in this note, and many similar cases, have been quenched at -78 °C with TFA, but results were essentially unchanged from a 0 °C quench.