Electron-transfer nucleophilic substitution reactions on neopentyl- and phenyl-substituted alkyl chlorides. Effect of the bridge length on the intramolecular electron-transfer catalysis

Journal of Organic Chemistry

Volumn 64, Issue 8, 1999, Pages 2626-2629

  Duca Jr , José S ^a   Gallego, Mariana H ^a   Pierini, Adriana B ^a   Rossi, Roberto A ^a  

^a DEPARTAMENTO DE FISICOQUÍMICA   (Argentina)

Author keywords

[No Author keywords available]

Indexed keywords

AMMONIA; ANION; BIPHENYL; CHLORIDE; METHYL GROUP; PENTANE; PHENYL GROUP; PHOSPHINE DERIVATIVE; RADICAL;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CYCLIZATION; DISSOCIATION; ELECTRON TRANSPORT; IRRADIATION; MOLECULAR INTERACTION; REACTION ANALYSIS;

EID: 0033574389     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo980657r     Document Type: Article

References (50)

1. March, J. Advanced Organic Chemistry, 4th ed.; John Wiley & Sons: New York, 1992. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, 3rd ed.; Plenum Press: New York, 1990, Part A.
2. March, J. Advanced Organic Chemistry, 4th ed.; John Wiley & Sons: New York, 1992. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, 3rd ed.; Plenum Press: New York, 1990, Part A.
3. RN1, see: (a) Rossi, R. A.; Pierini, A. B.; Palacios, S. M. Advances in Free Radical Chemistry; Tanner, D. D., Ed.; JAI Press: Greenwich, CT, 1990; p 193; J. Chem. Educ. 1989, 66, 720.
4. RN1, see: (a) Rossi, R. A.; Pierini, A. B.; Palacios, S. M. Advances in Free Radical Chemistry; Tanner, D. D., Ed.; JAI Press: Greenwich, CT, 1990; p 193; J. Chem. Educ. 1989, 66, 720.
5. (b) Saveánt, J. M. Adv. Phys. Org. Chem. 1990, 26, 1.
6. (c) Rossi, R. A.; Pierini, A. B.; Peñéñory, A. B. In The Chemistry of Functional Group; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, 1995; Supl. D2, Chapter 24.
7. (a) Bornancini, E. R. N.; Palacios, S. M.; Peñéñory, A. B.; Rossi, R. A. J. Phys. Org. Chem. 1989, 2, 255.
8. (b) Pierini, A. B.; Peñéñory, A. B.; Rossi, R. A. J. Org. Chem. 1985, 50, 2739.
9. Peñeñory, A. B.; Rossi, R. A. Gazz. Chim. Ital. 1995, 125, 605.
10. Nazareno, M. A.; Rossi, R. A. J. Org. Chem. 1996, 61, 1645.
11. (a) Savéant, J. M. J. Am. Chem. Soc. 1992, 114, 10595.
12. (b) Saveánt, J. M. Acc. Chem. Res. 1993, 26, 455.
13. (c) Compton, R. N.; Reinhart, P. W.; Cooper, C. C. J. Chem. Phys. 1978, 68, 4360.
14. (d) Raymonda, J. M.; Edwards, L. O.; Russel, B. B. J. Am. Chem. Soc. 1974, 96, 1708.
15. (a) Beckwith, A. L. J.; Palacios, S. M. J. Phys. Org. Chem. 1991, 4, 404.
16. (b) Ashby, E. C.; Gurumurthy, R.; Ridlehuber, R. W. J. Org. Chem. 1993, 58, 5832.
17. (c) Ashby, E. C.; Deshpande, A. K. J. Org. Chem. 1994, 59, 7358.
18. Santiago, A. N.; Takeuchi, K.; Ohga, Y.; Nishida, M.; Rossi, R. A. J. Org. Chem. 1991, 56, 1581.
19. Lukach, A. E.; Morris, D. G.; Santiago, A. N.; Rossi, R. A. J. Org. Chem. 1995, 60, 1000.
20. Experimental and theoretical data have been used to support the existence of π and σ radical anions. See: (a) Clarke, D. D.; Coulson, C. A. J. Chem. Soc. A 1969, 169.
21. (b) Dressler, R.; Allan, M.; Haselbach, E. Chimia 1985, 39, 385.
22. (c) Symons, M. C. R. Acta Chem. Scand. 1997, 51, 127.
23. (d) Pierini, A. B.; Duca, J. S., Jr. J. Chem. Soc., Perkin Trans. 2 1995, 1821.
24. (e) Casado, J.; Gallardo, I.; Moreno, M. J. Electroanal. Chem. 1987, 219, 197.
25. (f) Andrieux, C. P.; Savéant, J. M.; Zann, D. Nouv. J. Chim. 1984, 8, 107.
26. (a) Newton, M. D. Chem. Rev. 1991, 91, 767.
27. (b) Jordan, K. D.; Paddon-Row, M. N. Chem. Rev. 1992, 92, 395.
28. (c) Paddon-Row, M. N. Acc. Chem. Res. 1994, 27, 18.
29. (d) Kuki, A. Structure and Bonding; Springer-Verlag: Berlin, 1991; p 50.
30. (e) Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265.
31. (f) Isied, S. S.; Ogawa, M. Y.; Wishart, J. F. Chem. Rev. 1992, 92, 381.
32. (g) Beratan, D. N.; Betts, J. N.; Onuchic, J. N. Science 1991, 252, 12.
33. t are concentration at time t of both substrates. This equation is based on a first-order reaction of both substrates with the nucleophile. See: Bunnett, J. F. In Investigation of Rates and Mechanisms of Reaction, 3rd ed.; Lewis, E. S., Ed.; Wiley-Interscience: New York, 1974; part 1, p 159.
34. All the calculations were carried out with complete geometry optimization, and the semiempirical AM1 method as implemented in AMPAC. See: Liotard, D. A.; Healy, E. F.; Ruiz, J. M.; Dewar, M. J. S. AMPAC version 2.1, Quantum Chemistry Program Exchange program 506. QCPE Bull. 1989, 9, 123.
35. Pierini, A. B.; Santiago, A. N.; Rossi, R. A. Tetrahedron 1991, 47, 941.
36. (a) The AM1/UHF stationary points were characterized by calculating their Hessian matrix, no negative eigenvalue for a minimun energy structure, and one negative eigenvalue for a transition state. (b) The CI calculations were performed with the AM1/RHF Hamiltonian within the subspace of all possible excitations of five electrons into five molecular orbitals, from SOMO-2 up to SOMO+2 (CI = 5).
37. (a) Bertran, J.; Gallardo, I.; Moreno, M. Saveánt, J. M. J. Am. Chem. Soc. 1992, 114, 9576.
38. (b) Tikhomirov, V. A.; German, E. D.; Kuznetsov, A. M. Chem. Phys. 1995, 191, 25.
39. (c) Benassi, R.; Bertarini, C.; Taddei, F. Chem. Phys. Lett. 1996, 257, 633.
40. (d) Clark, T. Faraday Discuss. Chem. Soc. 1984, 78, 203.
41. (e) Hotokka, M.; Roos, B. O.; Eberson, L. J. Chem. Soc., Perkin Trans. 2 1986, 1979.
42. (f) Canadell, E.; Karafiloglou, P.; Salem. L. J. Am. Chem. Soc. 1980, 102, 855.
43. 9 at 298 K. See: Formosinho, S. J.; Arnaut, L. G. Bull. Chem. Soc. Jpn. 1997, 70, 977. For exchange reaction of other aromatic radical anions, see: Ward, R. L.; Weissman, S. I. J. Am. Chem. Soc. 1954, 76, 3612. Bergman, I. Trans. Faraday Soc. 1954, 50, 829.
44. 9 at 298 K. See: Formosinho, S. J.; Arnaut, L. G. Bull. Chem. Soc. Jpn. 1997, 70, 977. For exchange reaction of other aromatic radical anions, see: Ward, R. L.; Weissman, S. I. J. Am. Chem. Soc. 1954, 76, 3612. Bergman, I. Trans. Faraday Soc. 1954, 50, 829.
45. 9 at 298 K. See: Formosinho, S. J.; Arnaut, L. G. Bull. Chem. Soc. Jpn. 1997, 70, 977. For exchange reaction of other aromatic radical anions, see: Ward, R. L.; Weissman, S. I. J. Am. Chem. Soc. 1954, 76, 3612. Bergman, I. Trans. Faraday Soc. 1954, 50, 829.
46. 5b, ≅ 1 under high dilution, conditions where the equilibrium is not attained, according to simulations performed with the program Chemical Kinetics Simulator 1.01 (International Business Machines Corporation, 1996). We were unable to reach this limit experimentally.
47. t)
48. Bordwell, F. G.; Pitt, B. M.; Knell, N. J. Am. Chem. Soc. 1951, 73, 5004. Beringer, F. M.; Schultz, H. S. J. Am. Chem. Soc. 1955, 77, 5533.
49. Bordwell, F. G.; Pitt, B. M.; Knell, N. J. Am. Chem. Soc. 1951, 73, 5004. Beringer, F. M.; Schultz, H. S. J. Am. Chem. Soc. 1955, 77, 5533.
50. Stephenson, B.; Solladié, G.; Mosher, H. S. J. Am. Chem. Soc. 1972, 94, 4184.