Oxygen versus carbon acidity in the side-chain fragmentation of 2-, 3-, and 4-arylalkanol radical cations in aqueous solution: The influence of the distance between the OH group and the aromatic ring

Journal of the American Chemical Society

Volumn 121, Issue 28, 1999, Pages 6624-6629

  Baciocchi, Enrico ^a   Bietti, Massimo ^b   Manduchi, Laura ^a   Steenken, Steen ^c  

^a SAPIENZA UNIVERSITY OF ROME   (Italy)

^b UNIVERSITY OF ROME TOR VERGATA   (Italy)

^c MAX PLANCK INSTITUTE FOR CHEMICAL ENERGY CONVERSION   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANOL; AROMATIC COMPOUND; CARBON; CATION; HYDROXYL GROUP; OXIDIZING AGENT; OXYGEN;

ACIDITY; AQUEOUS SOLUTION; ARTICLE; CHEMICAL REACTION KINETICS; DEGRADATION; RADIOLYSIS; REACTION ANALYSIS;

EID: 0033591923     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990352+     Document Type: Article

References (32)

1. Baciocchi, E.; Bietti, M.; Steenken, S. J. Am. Chem. Soc. 1997, 119, 4078-4079.
2. Baciocchi, E.; Bietti, M.; Steenken, S. Chem. Eur. J. 1999, 5, 1785-1793.
3. Baciocchi, E.; Bietti, M.; Lanzalunga, O.; Steenken, S. J. Am. Chem. Soc. 1998, 120, 11516-11517.
4. Snook, M. E.; Hamilton, G. A. J. Am. Chem. Soc. 1974, 96, 860-869.
5. Davies, M. J.; Gilbert, B. C. Adv. Detailed React. Mech. 1991, 1, 35-81 and references therein.
6. Walling, C.; El-Taliawi, G. M.; Zhao, C. J. Org. Chem. 1983, 48, 4914-4917.
7. For a description of this technique see: O'Neill, P.; Steenken, S.; Schulte-Frohlinde, D. J. Phys. Chem. 1975, 79, 2773-2777.
8. Baciocchi, E.; Bietti, M.; Putignani, L.; Steenken, S. J. Am. Chem. Soc. 1996, 118, 5952-5960.
9. Neta, P.; Madhavan, V.; Zemel, H.; Fessenden, R. W. J. Am. Chem. Soc. 1977, 99, 163-164.
10. 2OH (formed by H-atom abstraction from 2-methyl-2-propanol by the OH radical), leading to the parent substrate and a carbocation. Thus in some cases the product study was carried out by generating the radical cation by reaction of the substrate with Co(III)W.
11. Baciocchi, E.; Bietti, M.; Steenken, S. J. Chem. Soc., Perkin Trans. 2 1996, 1261-1263.
12. Bietti, M.; Baciocchi, E.; Steenken, S. J. Phys. Chem. A 1998, 102, 7337-7342.
13. Eberson, L. J. Am. Chem. Soc. 1983, 105, 3192-3199.
14. Baciocchi, E.; Bietti, M.; Mattioli, M. J. Org. Chem. 1993, 58, 7106-7110.
15. •+8.
16. Faria, J. L.; Steenken, S. J. Phys. Chem. 1992, 96, 10869-10874.
17. 10
18. Gilbert, B. C.; Warren, C. J. Res. Chem. Intermed. 1989, 11, 1-17.
19. 10
20. a value of 17.4 for 2,4,6-trimethy-benzyl alcohol: Deno, N. C.; Jaruzelski, J. J.; Schriesheim, A. J. Am. Chem. Soc. 1955, 77, 3044-3051.
21. Ci, X.; Whitten, D. G. J. Am. Chem. Soc. 1989, 111, 3459-3461. See also: Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292- 297.
22. Ci, X.; Whitten, D. G. J. Am. Chem. Soc. 1989, 111, 3459-3461. See also: Gaillard, E. R.; Whitten, D. G. Acc. Chem. Res. 1996, 29, 292-297.
23. Burton, R. D.; Bartberger, M. D.; Zhang, Y.; Eyler, J. R.; Schanze, K. S. J. Am. Chem. Soc. 1996, 118, 5655-5664 and references therein.
24. 26
25. Wayner, D. D. M.; McPhee, D. J.; Griller, D. J. Am. Chem. Soc. 1988, 110, 132-137.
26. 29
27. See for example: Kiser, R. W. Introduction to Mass Spectrometry and its Applications; Prentice Hall: Englewood Cliffs, 1965; pp 308-320.
28. Fukuzumi, S.; Kochi, J. K. J. Am. Chem. Soc. 1981, 103, 7240-7252.
29. Mehta, L. K.; Porssa, M.; Parrick, J.; Candeias, L. P.; Wardman, P. J. Chem. Soc., Perkin Trans. 2 1997, 1487-1491.
30. 20 Probably, when the radical cation is p-methoxy substituted a significant portion of the charge resides on the OMe group. Thus, the intramolecular electron transfer, either outer- or inner-sphere, associated to the oxygen acidity, requires more energy and hence can efficiently occur only if there is deprotonation at the OH group.
31. Jagannadham, V.; Steenken, S. J. Am. Chem. Soc. 1984, 106, 6542-6551.
32. Schuler, R. H.; Hartzell, A. L.; Behar, B. J. Phys. Chem. 1981, 85, 192-199.