Poly methoxy phenols in solution: O-H bond dissociation enthalpies, structures, and hydrogen bonding

Journal of Organic Chemistry

Volumn 64, Issue 19, 1999, Pages 6969-6975

  De Heer, Martine I ^a   Korth, Hans Gert ^b   Mulder, Peter ^a  

^a LEIDEN UNIVERSITY   (Netherlands)

^b UNIVERSITY OF DUISBURG ESSEN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

2,4 DIMETHOXYPHENOL; 2,4,6 TRIMETHOXYPHENOL; GUAIACOL; MEQUINOL; PHENOL DERIVATIVE; SYRINGOL; UBIQUINONE; UNCLASSIFIED DRUG;

ANTIOXIDANT ACTIVITY; ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; DISSOLUTION; ENTHALPY; HYDROGEN BOND; MOLECULAR INTERACTION; MOLECULAR MODEL; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0033578691     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9901485     Document Type: Article

References (56)

1. For a recent review on BDE(O-H) values of substituted phenols, see: Borges dos Santos, R. M.; Martinho Simões, J. A. J. Phys. Chem. Ref. Data 1998, 27, 707-39.
2. Potterat, O. Curr. Org. Chem. 1997, 1, 415-40.
3. Wayner, D. D. M.; Lusztyk, E.; Ingold, K. U.; Mulder, P. J. Org. Chem. 1996, 61, 6430-3.
4. 3,7
5. Avila, D. V.; Ingold, K. U.; Lusztyk, J.; Green, W. H.; Procopio, D. R. J. Am. Chem. Soc. 1995, 117, 2929-30.
6. (a) Spencer, J. N.; Robertson, K. S.; Quick, E. E. J. Phys. Chem. 1974, 78, 2236-40.
7. (b) Khafizov, F. T.; Breus, V. A.; Kiselev, O. E.; Solomonov, B. N.; Konovalov, A. I. Zh. Obshch. Khim. 1990, 60, 721-30.
8. Skvortsov, I. M.; Fedorov, E. E.; Mushtakova, S. P. Zh. Fiz. Khim. 1986, 60, 2065-6.
9. Carlson, G. L.; Fateley, W. G. J. Phys. Chem. 1973, 77, 1157-63.
10. (e) Denisov, G. S.; Sheikh-Zade, M. I.; Éskina, M. V. Zh. Prikl. Spektrosk. 1977, 27, 1049-54.
11. Wayner, D. D. M.; Lusztyk, E.; Pagé, D.; Ingold, K. U.; Mulder, P.; Laarhoven, L. J. J.; Aldrich, H. S. J. Am. Chem. Soc. 1995, 117, 8737-44.
12. Laarhoven, L. J. J.; Mulder, P.; Wayner, D. D. M. Acc. Chem. Res. 1999, 32, 342-9.
13. 7
14. 12
15. NIST Standard Reference Database 25. Structures and Properties Database and Estimation Program. Version 2.01, 1994.
16. Diogo, H. P.; Minas da Piedade, M. E.; Martinho Simões, J. A.; Nagano, Y. J. Chem. Thermodyn. 1995, 27, 597-604.
17. -1 at the applied concentration of 0.03 M.
18. de Heer, M. I.; Korth, H. G.; Ingold, K. U.; Lusztyk, J.; Mulder, P. To be published.
19. solv(He).
20. Wilhelm, E.; Battino, R. Chem. Rev. 1973, 73, 1-9.
21. Epley, T. D.; Drago, R. S. J. Am. Chem. Soc. 1967, 89, 5770-3.
22. Arnett, E. M.; Joris, L.; Mitchell, E.; Murty, T. S. S. R.; Gorrie, T. M.; Schleyer, P. v. R. J. Am. Chem. Soc. 1970, 92, 2365-77.
23. Brinck, T.; Haeberlein, M.; Jonsson, M. J. Am. Chem. Soc. 1997, 119, 4239-44.
24. -1.
25. -1 compared to 8a).
26. -1) has both methoxy groups directed toward the oxygen.
27. -1 compared to 9a).
28. Tripathi, G. N. R.; Schuler, R. H. Chem. Phys. Lett. 1983, 98, 594-6.
29. Tripathi, G. N. R.; Schuler, R. H. J. Phys. Chem. 1988, 92, 5129-33.
30. -1, respectively. These values deviate from the experimental ΔBDEs known for these compounds, but illustrate clearly that substituent effects are similar for anisoles and phenols.
31. Wu, Y.-D.; Lai, D. K. W. J. Org. Chem. 1998, 61, 7904-10.
32. Schraa, G.-J.; Arends, I. W. C. E.; Mulder, P. J. Chem. Soc., Perkin Trans. 2 1994, 189-97.
33. Suryan, M. M.; Kafafi, S. A.; Stein, S. E. J. Am. Chem. Soc. 1989, 111, 1423-9.
34. -1, high compared to our results and also higher than can reasonably be expected for this bond. Possibly the conformation for the non-hydrogen-bonded molecule used in these calculations was not the lowest energy conformer, but the conformation with the methyl of the methoxy group directed toward the hydroxy group (see also ref 20).
35. Wright, J. S.; Carpenter, D. J.; McKay, D. J.; Ingold, K. U. J. Am. Chem. Soc. 1997, 119, 4245-52.
36. (a) Mulder, P.; Saastad, O. W.; Griller, D. J. Am. Chem. Soc. 1988, 110, 4090-2.
37. (b) Bordwell, F. G.; Zhang, X.-M.; Satish, A. V.; Cheng, J.-P. J. Am. Chem. Soc. 1994, 116, 6605-10.
38. Jonsson, M.; Lind, J.; Erikson, T. E.; Merényi, G. J. Chem. Soc., Perkin Trans. 2 1993, 1567-8.
39. -1, respectively, which is attributed to the formation of a second intramolecular hydrogen bond. This means that substitution with methoxy groups is purely additive and confirms that the polar effect in the closed shell molecules is small.
40. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165-95.
41. March J. Advanced Organic Chemistry: Reactions, Mechanisms, and Structure; McGraw-Hill, Inc.: New York, 1968; 241pp.
42. Lucarini, M.; Pedrielli, P.; Pedulli, G. F.; Cabiddu, S.; Fattuoni, C. J. Org. Chem. 1996, 61, 9259-63.
43. 37
44. van Scheppingen, W. B.; Dorrestijn, E.; Arends, I. W. C. E.; Mulder, P.; Korth, H.-G. J. Phys. Chem. A 1997, 101, 5404-11.
45. Jaffé, H. H. J. Am. Chem. Soc. 1957, 79, 2373-5.
46. Spencer, J. N.; Heckman, E. A.; Harner, R. S.; Shoop, S. L.; Robertson, K. S. J. Phys. Chem. 1973, 77, 3103-6.
47. inter-HB values for the formation of the additional hydrogen bond between intramolecularly hydrogen bonded 2-methoxyphenol and the solvent molecules, the change in concentration of C could probably not be detected by the IR method and concentrations used, except with the strongest hydrogen-bond acceptor DMSO.
48. Banks, J. T.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1996, 118, 6790-1.
49. inter-HB is an apparent value, since the chemical potential (activity coefficient) changes when the concentration of solute increases (i.e., going to pure ethyl acetate).
50. -1, and consequently, the free phenol concentration in water will be as low as 0.03%.
51. Courty, A.; Mons, M.; Dimicoli, I.; Piuzzi, F.; Brenner, V.; Millié, P. J. Phys. Chem. A 1998, 102, 4890-8.
52. -1. For the formation of the additional intermolecular hydrogen bond of C and ethyl acetate the entropy change is expected to be the same.
53. Khafizov, F. T.; Breus, V. A.; Solomonov, B. N.; Kiselev, O. E.; Konovalov, A. I. Dokl. Akad. Nauk SSSR 1988, 303, 916-9.
54. Foti, M.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 9440-7.
55. Matsumoto, M.; Kobayashi, H.; Hotta, Y. J. Org. Chem. 1984, 49, 4740-1.
56. Scott, P. A.; Radom, L. J. Phys. Chem. 1996, 100, 16502-13.