A Generalized Treatment of Substituent Effects in the Benzene Series. A Statistical Analysis by the Dual Substituent Parameter Equation (1)

Progress in Physical Organic Chemistry

Volumn 10, Issue , 2007, Pages 1-80

  Ehrenson, S ^a,b   Brownlee, R T C ^a,b   Taft, R W ^a,b  

^a BROOKHAVEN NATIONAL LABORATORY   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Fittings; Ionization; M substituent effects; Phenols; Separation

Indexed keywords

IONIZATION; PHENOLS; SEPARATION;

DUAL SUBSTITUENT PARAMETERS; SUBSTITUENT EFFECT;

PIPE FITTINGS;

EID: 84983724354     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9780470171899.ch1     Document Type: Chapter

References (70)

1. This work was supported in part by the National Science Foundation (UCI) and the U.S. Atomic Energy Commission (Brookhaven).
2. For previous treatments, cf. the following:Hammett, L. P. Chem. Rev., 17, 125 (1935)
3. Jaffe, H. H., Chem. Rev., 53, 191 (1953)
4. Brown, H. C, and Y. Okamoto, J. Am. Chem. Soc., 79, 1913 (1957)
5. McDaniel, D. H., and H. C. Brown, J. Org. Chem., 23, 425 (1958)
6. van Bekkum, H., P. E. Verkade, and B. M. Wepster, Rec. Trav. Chim., 78, 815 (1959)
7. Taft, R. W., and I. C. Lewis, J. Am. Chem. Soc, 81, 5343 (1959)
8. Yukawa, Y., and Y. Tsuno, Bull. Chem. Soc. Japan, 32, 965, 971 (1959)
9. Roberts, J. L., and H. H. Jaffe,J. Am. Chem. Soc, 81, 1635 (1959)
10. Taft, R. W., J. Phys. Chem., 64, 1805 (1960)
11. Palm, V., Russ. Chem. Rev., 31, 471 (1961)
12. Wells, P. R., Chem. Rev., 63, 171 (1963)
13. Ehrenson, S., Prog. Phys. Org. Chem., 2, 195 (1964)
14. Ritchie, C. D., and W. F. Sager, Prog. Phys. Org. Chem., 2, 323 (1964)
15. Charton, U.,J. Am. Chem. Soc, 86, 2033 (1964)
16. Exner, O., Collection Czech. Chem. Commun., 31, 65 (1966)
17. Wells, P. R., S. Ehrenson, and R. W. Taft, Prog. Phys. Org. Chem., 6, 147 (1968)
18. Swain, C. G., and E. C. Lupton, Jr., J. Am. Chem. Soc, 90, 4328 (1968)
19. Hammett, L. P., Physical Organic Chemistry, McGraw-Hill, 2nd ed., 1970, Chap. 11.
20. Taft, R. W., J. Am. Chem. Soc, 79, 1045 (1957)
21. cf. also references 2(1), p. 244 and 2(p), p. 191, for background discussions.
22. Taft, R. W., in N. S. Newman, Steric Effects in Organic Chemistry, Wiley, New York, 1956, Ch. 13; cf. reference (3a), footnote (4), for clarification of symbolism.
23. cf. references 2(f) and 2(h); E. D. Schmid, et al, Spectrochim. Acta, 22, 1615, 1621, 1633, 1645,1659 (1966).
24. Rakshys, J. W., R. W. Taft, and W. A. Sheppard, J. Am. Chem. Soc, 90, 5236 (1968).
25. References 2(a), 2(c), 2(e), and 2(f)
26. R. W. Taft, S. Ehrenson, I. C. Lewis, and R. E. Glick,J. Am. Chem. Soc, 81, 5352 (1959).
27. 5, Ray, N. H., J. Chem. Soc, 1440 (1963)
28. 3SO, Orda, V. V., L. M. Yogupolskii, V. F. Bystrov, and A. U. Stepanyants,J. Gen. Chem., 35, 1631 (1965)
29. Ionization of 4-substituted [2.2.2.] octane-1 carboxylic acids, 4-substituted bicyclo [2.2.2.] octa-2-ene-l-carboxylic acids and dibenzobicyclo [2.2.2.] octa-2,5-diene-l-carboxylic acids, 50% aq. EtOH, 25°, Baker, F. W., R. C. Parish, and L. M. Stock,J. Am. Chem. Soc, 89, 5677 (1967)
30. Ionization of 4-substituted bicyclo [2.2.2.] octane-1-carboxylic acids and 4-substituted bicyclo [2.2.1] heptane-l-carboxylic acids in 50% aq. MeOH, 25°, Wilcox, C. F., and C. Leung, J. Am. Chem. Soc, 90, 336 (1968).
31. Fawcett, F. S., and W. A. Sheppard,J. Am. Chem. Soc, 87, 4341 (1955).
32. Taft, R. W., E. Price, I. R. Fox, I. C. Lewis, K. K. Andersen, and G.T. Davis, J. Am. Chem. Soc, 85, 709, 3146 (1963).
33. Angelelli, J. M., R. T. C. Brownlee, A. R. Katritzky, R. D. Topsom, and L. Yakhontov, /. Am. Chem. Soc, 91, 4500 (1969).
34. We are indebted to Dr. Douglas Blagdon for drawing our attention to these data.
35. Tanida, H., Y. Hata, S. Ikegami, and H. Ishitobi, J. Am. Chem. Soc, 89, 2928 (1967).
36. Brownlee, R. T. C, A. R. Katritzky, and R. D. Topsom,J. Am. Chem. Soc, 87, 3261 (1965)
37. Katritzky, A. R., R. F. Pinzelli, M. V. Sinnott, and R. D. Topsom,J. Am. Chem. Soc, in press.
38. Brown, H. C.and Y. Okamoto,J. Am. Chem. Soc, 80, 4980 (1958).
39. Yukawa, Y., Y. Tsuno, and M. Sawada, Bull. Chem. Soc. Japan, 39, 2274 (1966).
40. Eaborn, C, J. Chem. Soc, 4858 (1956)
41. Dean, E. B., and C. Eaborn, J. Chem. Soc, 2299 (1959)
42. Private communication from Professor Eaborn.
43. Presentation of Professor Y. Yukawa at Second Linear Free Energy Conference, Irvine, California, March 1968.
44. Brownlee, R. T. C, and R. W. Taft, J. Am. Chem. Soc, 90, 6537 (1968);J. Am. Chem. Soc, 92, 7007 (1970)
45. Taft, R. W., N. C. Deno, and P. S. Skell, Ann. Rev. Phys. Chem., 9, 287 (1958).
46. Streitwieser, A., Jr., and H. F. Koch, J. Am. Chem. Soc, 86, 404 (1964)
47. McKeever, L. D., and R. W. Taft, J. Am. Chem. Soc, 88, 4544 (1966).
48. Craig, D. P., J. Chem. Soc, 997 (1959)
49. Bordwell, F. G., and P. J. Boutan, J. Am. Chem. Soc, 78, 87 (1956).
50. Taft, R. W., and J. W. Rakshys, Jr., J. Am. Chem. Soc, 87, 4387 (1965).
51. Pews, R. G., Y. Tsuno, and R. W. Taft,J. Am. Chem. Soc, 89, 2391 (1967).
52. Ramsey, N. F., Phys. Rev., 78, 699 (1950)
53. Pople, J. A., and M. Karplus, J. Chem. Phys., 38, 2803 (1963).
54. Exner, O., and J. Jonas, Coll. Czech. Chem. Commun., 27, 2296 (1962).
55. Bunnett, J. F., and E. Zahler, Chem. Revs., 49, 273 (1951)
56. Lewis, E. S., and E. B. Miller, J. Am. Chem. Soc, 75, 429 (1953)
57. Dickson, J. D., and C. Eaborn,J. Chem. Soc, 3036 (1959). These authors first point out that the rates of aqueous decomposition of p- and m-substituted phenyldiazonium salts could be described by an equation of the form of eq. (1).
58. Gutbezahl, B., and E. Grunwald, J. Am. Chem. Soc, 75, 559 (1953).
59. cf., however, reference 20.
60. Holtz, D.,Prog. Phys. Org. Chem., 8, 55 (1971).
61. Nelson, J. H., R. G. Harvey, and R. D. Ragsdale,J. Hetero. Chem., 4, 591 (1967).
62. Eaborn, C, H. L. Hornfeld, and D. R. M. Walton,J. Chem. Soc. (B), 1036 (1967).
63. Latta, B. M., and R. W. Taft,J. Am. Chem. Soc, 89, 5172 (1967).
64. Kirkwood, J. G., and F. H. Westheimer, J Chem.Phys., (5,506,513(1938).
65. Charton, M., Prog. Phys. Org. Chem., 8, 235 (1971) has reported extensively on correlations of rate data for ortho substituted benzene derivatives using the dual substituent parameter treatment in the form with an additional (intercept) parameter, and in our opinion, too limited substituent data sets. For these and related reasons which we have discussed, we question the significance of many of Charton's correlations.
66. M. Charton has summarized his earlier correlations of these data in reference 35. Our results are dissimilar to those of Charton for the reasons indicated.
67. Charton, M., and B. I. Charton,J. Org. Chem., 33, 3872 (1968)
68. Bowden, K., N. B. Chapman, and J. Shorter,J. Chem. Soc, 5239 (1963)
69. Bowden, K., M. Hardy, and D. C. Parkin, Can. J. Chem., 46, 2929 (1968).
70. Shatenshtein, A. I., Adv. Phys. Org. Chem., 1, 155 (1963).