Ambident reactivity of enolate ions toward 1,3,5-trinitrobenzene. The first observation of an oxygen-bonded enolate Meisenheimer complex

Journal of the American Chemical Society

Volumn 118, Issue 25, 1996, Pages 6072-6073

  Buncel, Erwin ^a   Dust, Julian M ^a,b   Manderville, Richard A ^a,c  

^a QUEEN S UNIVERSITY   (Canada)

^b MEMORIAL UNIVERSITY OF NEWFOUNDLAND   (Canada)

^c WAKE FOREST UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

NITROBENZENE DERIVATIVE;

ARTICLE; COMPLEX FORMATION; REACTION ANALYSIS;

EID: 0030058990     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960590u     Document Type: Article

References (42)

1. (a) Buncel, E. In The Chemistry of Amino, Nitro and Nitroso Compounds. Supplement F; Patai, S., Ed.; Wiley: London, 1982.
2. (b) Buncel, E.; Crampton, M. R.; Strauss, M. J.; Terrier, F. Electron Deficient Aromatic-and Heteroaromatic-Base Interactions. The Chemistry of Anionic Sigma Complexes; Elsevier: Amsterdam, 1984; pp 244-250.
3. (c) Artamkina, G. A.; Egorov, M. P.; Beletskaya, I. P. Chem. Rev. 1982, 82, 427.
4. (d) Bernasconi, C. A. MTP Int. Rev. Sci., Org, Chem. Ser. 1. 1973, 3, 33.
5. (e) Strauss, M. J. Chem. Rev. 1970, 70, 667.
6. (f) Crampton, M. R. Adv. Phys. Org. Chem. 1969, 7, 211.
7. (a) Janovsky, J. V.; Erb, L. Chem. Ber. 1886, 19, 2115.
8. (b) Mahacek, V.; Sterba, A.; Lycka, A.; Snoble, D. J. Chem. Soc., Perkin Trans. 2 1982, 355.
9. Kovar, K. A. Pharm. Unserer. Z 1972, 1, 17.
10. (a) Terrier, F. Chem. Rev. 1982, 82. 77.
11. (b) Murphy, R. M.; Wulff, C. A.; Strauss, M. J. J. Am. Chem. Soc. 1974, 96, 2678.
12. (c) Fendler, J, H.; Hinze, W. L.; Liu, L. J. Chem. Soc., Perkin Trans. 2 1975, 1768.
13. Strauss, M. J. Acc. Chem. Res. 1974, 7, 181.
14. Bacaloglu, R.; Bunton, C. A.; Ortega, F. J. Am. Chem. Soc. 1989, 111, 1041.
15. Houk, K. N.; Paddon-Row, M. N. J. Am. Chem. Soc. 1988, 110, 2706.
16. (a) Brickhouse, M. D.; Squires, R. R. J. Phys. Org. Chem. 1989, 2, 329.
17. (b) Freriks, I. L.; de Koning, L. J.; Nibbering, N. M. M. J. Am. Chem. Soc. 1991, 113, 9119.
18. Zhong, M.; Brauman, J. I. J. Am. Chem. Soc. 1996, 118, 636.
19. (a) Buncel, E.; Dust, J. M.; Park, K. T.; Renfrow, R. A.: Strauss, M. J. In Nucleophilicity; Harris, J. M., McManus, S. P., Eds.: Advances in Chemistry Ser. 215; American Chemical Society: Washington, D.C., 1987: pp 369-383.
20. (b) Buncel, E.; Manderville, R. A. J. Phys. Org. Chem. 1993, 6, 71.
21. (c) Buncel, E.: Dust. J. M. Can. J. Chem. 1988, 66, 1712.
22. (d) Buncel, E.; Renfrow, R. A.; Strauss, M. J. J. Am. Chem. Soc: 1983, 105 2473.
23. (e) Buncel, E.: Dust, J. M.; Jonczyk, A.; Manderville, R. A.: Onyido, I. J. Am. Chem. Soc. 1992, 114, 5610.
24. (a) Buncel, E.: Dust, J. M.; Terrier, F. Chem. Rev. 1995, 95, 2261.
25. (b) Servis, K. J. Am. Chem. Soc. 1967, 89, 1508.
26. (c) Caveng. P.; Zollinger, H. Helv. Chim. Acta 1967, 50, 861.
27. (d) Norris, A. R. Can. J. Chem. 1969, 47, 2895.
28. (e) Bernasconi, C. F. J. Am. Chem. Soc. 1971, 93, 6975.
29. (f) Biggi, G.; Pietra, F. J. Chem. Soc. Perkin Trans. 1 1973, 1980.
30. (g) Crampton, M. R.; Stevens, J. A. J. Chem. Soc. Perkin Trans. 2 1990, 1097.
31. (h) Dust, J. M.; Harris, J. M. J. Polym. Sci., Part A: Polym. Chem. 1990, 28, 1875.
32. 3) to initiate the reaction. The potassium enolate likely exists in solution as "loose" ion pairs (Buncel, E.; Menon, B. C. J. Org. Chem. 1979, 44, 317; J. Am. Chem. Soc. 1980, 102, 3499). The potassium enolate and TNB were present in equimolar initial concentrations (0.06 M).
33. 3) to initiate the reaction. The potassium enolate likely exists in solution as "loose" ion pairs (Buncel, E.; Menon, B. C. J. Org. Chem. 1979, 44, 317; J. Am. Chem. Soc. 1980, 102, 3499). The potassium enolate and TNB were present in equimolar initial concentrations (0.06 M).
34. 3) to initiate the reaction. The potassium enolate likely exists in solution as "loose" ion pairs (Buncel, E.; Menon, B. C. J. Org. Chem. 1979, 44, 317; J. Am. Chem. Soc. 1980, 102, 3499). The potassium enolate and TNB were present in equimolar initial concentrations (0.06 M).
35. 3.5 8.26 (Taylor, R. P. Chem. Commun. 1970, 1463)).
36. The aryl-H signals are apparent triplets or doublets with unresolved coupling.
37. Other side reactions which could conceivably occur in this system include oxidation of the C-adduct to picryl acetophenone, in a formal hydride transfer. However, this process would be favored through using excess TNB, which could yield a variety of reduction products, whereas in the present study equimolar TNB and enolate were used. We thank a referee for bringing this to our attention.
38. 10; ambient temperature; 100.1 MHz) for 3 (refer to Scheme 1, structure 3 for numbering) are as follows: 37.4 (C-1), 133.7 (C-2,6), 126.4 (C-3,5), 123.4 (C-4), 43.1 (C-α), 198.5 (carbonyl), 138.8, 129.9, 129.4, 134.0 (pheryl ring of acetophenone enolate moiety).
39. Crampton, M. R.; Stevens, J. A. J. Chem. Soc., Perkin Trans. 2 1991, 1715.
40. We thank a referee for calling our attention to the possibility of isomerization via a pericyclic rearrangement.
41. (a) Burrows, C. J.; Carpenter, B. K. J. Am. Chem. Soc. 1981, 103, 6983.
42. (b) Wunderli, A.; Winkler, T.; Hansen, H. J. Helv. Chim. Acta 1977, 60, 2436.