Inductive effects in isolated molecules: 4-Substituted bicyclo[2.2.2]octane-1-carboxylic Acids

Chemistry - A European Journal

Volumn 8, Issue 22, 2002, Pages 5147-5152

  Exner, Otto ^a   Böhm, Stanislav ^b  

^a INSTITUTE OF ORGANIC CHEMISTRY AND BIOCHEMISTRY   (Czech Republic)

^b INSTITUTE OF CHEMICAL TECHNOLOGY   (Czech Republic)

Author keywords

Ab initio calculations; Acidity; Carboxylic acids; Inductive effect; Linear free energy relationships

Indexed keywords

ACIDITY; NEGATIVE IONS; PROBABILITY DENSITY FUNCTION; SUBSTITUTION REACTIONS;

ZERO DIPOLE MOMENT;

CARBOXYLIC ACIDS;

CARBOXYLIC ACID DERIVATIVE; OCTANE;

AB INITIO CALCULATION; ACIDITY; ARTICLE; DENSITY; DIPOLE; ELECTRICITY; MOLECULAR DYNAMICS; QUANTUM CHEMISTRY;

EID: 0037112594     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20021115)8:22<5147::AID-CHEM5147>3.0.CO;2-T     Document Type: Article

References (67)

1. a) C. K. Ingold, Structure and Mechanism in Organic Chemistry, Cornell University Press. Ithaca, NY. 1953, mainly Chapters 11-7, XIII-46c;
2. b) L. P. Hammett, Physical Organic Chemistry, McGraw-Hill, New York, 1970, p. 374:
3. c) J. Hine, Structural Effect on Equilibria in Organic Chemistry, Wiley, New York, 1975. Chapters 2-1, 2-2;
4. c) H. C. Brown, D. H. McDaniel, O. Häfliger, in Determination of Organic Structures by Physical Methods (Eds.: E. A. Braude, F. C. Nachod), Academic Press, New York. 1955, pp. 567-662.
5. a) F. A. Carey, Organic Chemitry, 3rd Ed., McGraw-Hill, New York, 1996, p. 139 and 770;
6. b) T. W. G. Solomons, Organic Chemistry, 5th Ed., Wiley, New York, 1992, p. 763.
7. J. D. Roberts, W. T. Moreland, Jr., J. Am. Chem. Soc. 1953, 75, 2167-2173.
8. M. Charton, Prog. Phys. Org. Chem. 1981, 13, 119-251.
9. a) R. W. Taft, Jr., J. Am. Chem. Soc. 1957, 79, 1045-1049;
10. b) O. Exner, J. Jonáš, Collect. Czech. Chem. Commun. 1962, 27, 2296-2306.
11. c) J. Paleèek, J. Hlavatý, Collect. Czech. Chem. Commun. 1973, 38, 1985-2002;
12. d) C. A. Grob, B. Schaub, M. G. Schlageter, Helv. Chim. Acta 1980, 63, 57-62;
13. e) A. Fischer, M. J. King, F. P. Robinson, Can. J. Chem. 1978, 56, 3059-3067;
14. f) A. Fischer, M. J. King, F. P. Robinson, Can. J. Chem. 1978, 56, 3068-3071;
15. g) A. Fischer, M. J. King, F. P. Robinson, Can. J. Chem. 1978, 56. 3072-3077.
16. C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165-195.
17. a) T. B. McMahon, P. Kebarle, J. Am. Chem. Soc. 1977, 99, 2222-2230;
18. b) R. W. Taft, R. D. Topsom, Prog. Phys. Org. Chem. 1987, 16, 1-83;
19. c) I. A. Koppel, M. Mishima, L. M. Stock, R. W. Taft, R. D. Topsom, J. Phys. Org. Chem. 1993, 6, 685-689.
20. a) W. J. Hehre, R. Ditchfield, L. Radom, J. A. Pople, J. Am. Chem. Soc. 1970, 92, 4796-4801;
21. P. George, M. Trachtman, C. W. Bock, A. M. Brett, J. Chem. Soc. Perkin Trans. 2 1976, 1222-1227.
22. A. Pross, L. Radom, R. W. Taft, J. Org. Chem. 1980, 45, 818-826.
23. O. Exner, Org. React. 1995, 29, 1-6.
24. O. Exner. P. Nauš, J. Phys. Org. Chem. 2000, 13, 693-698.
25. a) S. Marriott, R. D. Topsom, J. Am. Chem. Soc. 1984, 106, 7-10;
26. b) O. Exner, M. Ingr, P. Čársky, J. Mol. Struct. (THEOCHEM) 1997, 397, 231-238.
27. O. Exner, Org. React. 1984, 21, 3-26.
28. a) C. D. Ritchie, E. S. Lewis, J. Am. Chem. Soc. 1962, 84, 591-594;
29. b) H. D. Holtz, L. M. Stock, J. Org. Chem. 1964, 86, 5188-5194;
30. c) F. W. Baker, R. C. Parish, L. M. Stock, J. Am. Chem. Soc. 1967, 89, 5677-5685;
31. d) C. F. Wilcox Jr., J. S. McIntyre, J. Org. Chem. 1965, 30, 777-780.
32. a) Z. Friedl, J. Hapala, O. Exner, Collect. Czech. Chem. Commun. 1979, 44, 2928-2945;
33. b) W. Adcock, F. Anvia, G. Butt, A. Cook, P, Duggan, C. A. Grob, S. Marriott, J. Rowe, M. Taagepera, R. W. Taft, R. D. Topsom, J. Phys. Org. Chem. 1991, 4, 353-360;
34. c) W. Adcock, A. N. Abeywickrema, J. Org. Chem. 1982. 47, 2957-2966;
35. d) W. Adcock, A. N. Abeywickrema, V. S. Iyer, G. B. Kok, J. Am. Chem. Soc. 1983, 105, 290-292:
36. e) W. Adcock, A. N. Abeywickrema, Magn. Reson. Chem. 1986, 24, 213-220.
37. a) R. B. Hermann, J. Am. Chem. Soc. 1969, 91, 3152-3158;
38. b) N. Inamoto, S. Masuda, J. Niwa, Bull. Chem. Soc. Jpn. 1985, 58, 158-164.
39. a) O. Exner, Collect. Czech. Chem. Commun. 1966, 31, 65-89;
40. b) J. Shorter, Correlation Analysis of Organic Reactivity with Particular Reference to Multiple Regression, Research Studies Press, Wiley, Chichester, 1982, pp. 53-54;
41. c) W. F. Reynolds, Prog. Phys. Org. Chem. 1983, 14, 165-203;
42. d) M. Charton. Adv. Quant. Struct.-Prop. Relat. 1996, 1, 171-219.
43. A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652.
44. a) O. Exner, S. Böhm, J. Chem. Soc. Perkin Trans. 2 2000, 1994-1991;
45. b) M. Alcamí, O. Mó, M. Yáñez, J. Phys. Org. Chem. 2002, 15, 174-186.
46. O. Exner, S. Böhm, J. Org. Chem. 2002, 67, 6320-6327.
47. a) M. Decouzon, P. Ertl, O. Exner, J.-F. Gal, P.-C. Maria, J. Am. Chem. Soc. 1993, 115, 12071-12078;
48. b) M. Decouzon, J.-F. Gal, P.-C. Maria, S. Böhm, P. Jiménez, M. V. Roux, O. Exner, New J. Chem. 1997, 21, 561-573;
49. c) S. Bohm, O. Exner, Chem. Eur. J. 2000, 6, 3391-3398;
50. d) O. Exner, S. Böhm, M. Decouzon, J.-F. Gal, P.-C. Maria, J. Chem. Soc. Perkin Trans. 2 2002, 168-172.
51. A. Yokozeki, K. Kuchitsu, Y. Morino, Bull. Chem. Soc. Jpn. 1970, 43, 2017-2026.
52. -1 was achieved at the level MP2/6-311 ++ G**//B3LYP/6-311 + G*: K. B. Wiberg, J. Org. Chem. 2002, 67, 1613-1617. The difference might be partly due to a somewhat different choice of substituents. In our opinion, there is not sufficient evidence that the theoretical model chosen by us should be more efficient, although it might be a priori more consistent.
53. 1): acidities of meta- and para-substituted benzoic acids 2.37 (ref. [20]), basicities of alkyl-substituted pyridines 2.11 (ret [25a]), enthalpies of formation of isomeric dimethylbenzoic acids 2.58 (ref. [25b]). We attribute the differences mainly to the different accuracy of the experimental data.
54. a) J. Roithová, O. Exner, J. Phys. Org. Chem. 2001, 14, 752- 758:
55. S. Böhm, O. Exner, unpublished results.
56. L. R. Schmitz, K.-H. Chen. J. Labanowski, N. L. Allinger, J. Phys. Org. Chem. 2001, 14, 90-96.
57. O. Exner, S. Böhm, Collect. Czech. Chem. Commun. 2001, 66, 1623-1637.
58. a) O. Exner, J. Phys. Org. Chem. 1999, 12, 265-274:
59. b) M. Charton, J. Phys. Org. Chem. 1999, 12, 275-282;
60. c) K, Bowden, E. J. Grubbs, Chem. Soc. Rev. 1996, 25, 171-177.
61. C. S. Yoder, C. H. Yoder, J. Am. Chem. Soc. 1980, 102, 1245-1247.
62. M. A. P. Segurado, J. C. R. Reis, J. D. G. de Oliveira, J. Chem. Soc. Perkin Trans. 2 2002, 323-328.
63. An opposite opinion - that the electrostatic approach overestimates the effects of charged substituents - was based only on reactivities in solution: V. A. Palm, Reakts. Sposobn. Org. Soedin. 1968, 5, 583-600.
64. A) probably originates from ref. [28c], but is not essential since the results of calculations are correct.
65. We consider here the electrostatic calculations only as a tool for approximate prediction of the acidities. We do not discuss their function in defending the transmission "through space" versus the transmission "through bonds", refs. [17d, 28b,c, 34]. In our opinion (ref. [28a]), the problem is ill formulated.
66. M. Charton, B. I. Charton, J. Chem. Soc. Perkin Trans. 2 1999, 2203-2211.
67. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. J. P. Stewart, M. Head-Gordon, C. Gonzales, J. A. Pople, Gaussian 94, Revision C.3, Gaussian, Inc. Pittsburgh PA. 1995.