Photolysis and oxidation of azidophenyl-substituted radicals: Delocalization in heteroatom-based radicals

Journal of Organic Chemistry

Volumn 69, Issue 16, 2004, Pages 5247-5260

  Serwinski, Paul R ^a,b   Esat, Burak ^a,c   Lahti, Paul M ^a   Liao, Yi ^a,d   Walton, Richard ^a,e   Lan, Jiang ^a,f  

^a UNIVERSITY OF MASSACHUSETTS   (United States)

^b Sensor Research and Development Corp   (United States)

^c Gemsan AS   (Turkey)

^d UNIVERSITY OF WASHINGTON   (United States)

^e Ethox Chemicals LLC   (United States)

^f Verizon Laboratories   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRON SPIN RESONANCE SPECTROSCOPY; OXIDATION; PHOTOLYSIS; SALTS; SOLUTIONS; SUBSTITUTION REACTIONS;

DELOCALIZATION; NITRENO RADICALS;

FREE RADICALS;

(3 AZIDOPHENYL) N TERT BUTYL N AMINOXYL; 2 (3 AZIDOPHENYL) 4,4,5,5 TETRAMETHYL 4,5 DIHYDRO 1H IMIDAZOLE 3 OXIDE 1 OXYL; 2 (4 AZIDOPHENYL) 1,2,6 TRIPHENYLVERDAZYL; 2 (4 AZIDOPHENYL) 4,4,5,5 TETRAMETHYL 4,5 DIHYDRO 1H IMIDAZOLE 3 OXIDE 1 OXYL; 2 (4 AZIDOPHENYL)BENZIMIDAZOLE 1 OXIDE 3 OXYL; AZIDE; PERCHLORATE; PHENYL GROUP; RADICAL; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; COLUMN CHROMATOGRAPHY; CRYSTAL STRUCTURE; DENSITY FUNCTIONAL THEORY; ELECTRON SPIN RESONANCE; OXIDATION; PHOTOLYSIS; ULTRAVIOLET SPECTROSCOPY;

EID: 3542995078     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049500r     Document Type: Article

References (54)

1. (a) Longuet-Higgins, H. C. J. Chem. Phys. 1950, 18, 265, 275, 283.
2. (b) Longuet-Higgins, H. C. In Theoretical Organic Chemistry, Kekulé Symposium; Butterworth: London, 1958; p 9.
3. (c) Ovchinnikov, A. A. Theor. Chim. Acta 1978, 47, 297.
4. (d) Klein, D. J.; Nelin, C. J.; Alexander, S.; Matsen, F. E. J. Chem. Phys. 1982, 77, 3101.
5. (e) Klein, D. J. Pure Appl. Chem. 1983, 55, 299.
6. (f) Klein, D. J.; Alexander, S. A. In Graph Theory and Topology in Chemistry; King, R. B., Rouvray, D. H., Eds.; Elsevier: Amsterdam, The Netherlands, 1987; Vol. 51, p 404.
7. (g) Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587.
8. (h) Shen, M.; Sinanoglu, O. In Graph Theory and Topology in Chemistry; King, R. B., Rouvay, D. H., Eds.; Elsevier: Amsterdam, The Netherlands, 1987; Vol. 51, p 373.
9. (a) Dvolaitzky, M.; Chiarelli, R.; Rassat, A. Angew. Chem., Int. Ed. Engl. 1992, 31, 180.
10. (b) Kanno, F.; Inoue, K.; Koga, N.; Iwamura, H. J. Am. Chem. Soc. 1993, 115, 847.
11. (c) Borden, W. T.; Iwamura, H.; Berson, J. A. Acc. Chem. Res. 1994, 27, 109.
12. (d) Shultz, D. A.; Bodnar, S. H.; Lee, H.; Kampf, J. W.; Incarvito, C. D.; Rheingold, A. L. J. Am. Chem. Soc. 2002, 124, 10054.
13. (e) Shultz, D. A.; Fico, R. M., Jr.; Bodnar, S. H.; Kumar, R. K.; Vostrikova, K. E.; Kampf, J. W.; Boyle, P. D. J. Am. Chem. Soc. 2003, 125, 11761.
14. (f) Shultz, D. A.; Fico, R. M., Jr.; Lee, H.; Kampf, J. W.; Kirschbaum, K.; Pinkerton, A. A.; Boyle, P. D. J. Am. Chem. Soc. 2003, 125, 15426.
15. Inoue, K.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 927.
16. Matsuda, K.; Iwamura, H. Mol. Cryst. Liq. Cryst., Sect. A 1997, 306, 89.
17. Okada, K.; Imakura, T.; Oda, M.; Murai, H.; Baumgarten, M. J. Am. Chem. Soc. 1996, 118, 3047.
18. Rule, M.; Matlin, A. R.; Seeger, D. E.; Hilinski, E. F.; Dougherty, D. A.; Berson, J. A. Tetrahedron 1982, 38, 787.
19. Horvat, D. A.; Murcko, M. A.; Lahti, P. M.; Borden, W. T., J. Chem. Soc., Perkin 2, 1998, 1037.
20. (a) Tukada, H. Chem. Commun. 1993, 302.
21. (b) Tukada, H.; Mutai, K.; Iwamura, H. Chem. Commun. 1987, 1159.
22. (c) Cf. also meta-linkage of phenylnitrene to a localized biradical to give a heterospin quintet system in: Tukada, H. Org. Lett. 2001, 3, 3261.
23. (a) For 7, a preliminary study was described in: Esat, B.; Walton, R.; Lahti, P. M. J. Am. Chem. Soc. 1998, 120, 5122.
24. (b) Preliminary results for 8-11 were described in the proceedings of the VIIth International Conference on Molecular Magnetism: Lahti, P. M.; Esat, B.; Liao, Y.; Serwinski, P. R.; Lan, J.; Walton, R. Polyhedron 2001, 20, 1647. The ESR spectra for compounds 11 and 12 were inadvertently reverse labeled in that article: the zfs parameters were given correctly.
25. Wasserman, E. Prog. Phys. Org. Chem. 1971, 8, 319.
26. For an example of photochemical activation of bis(pyridyl)-carbenes to link paramagnetic cations, see: (a) Koga, N.; Ishimaru, Y.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1996, 35, 755.
27. (b) Sano, Y.; Tanaka, M.; Koga, N.; Matsuda, K.; Iwamura, H.; Rabu, P.; Drillon, M. J. Am. Chem. Soc. 1997, 119, 8246.
28. (a) Ovcharenko, V.; Fokin, S.; Rey, P. Mol. Cryst. Liq. Cryst. Sect. A 1999, 334, 109.
29. (b) Esat, B. Ph.D. Dissertation, University of Massachusetts, Amherst, MA, 2001.
30. (a) Balaban A. T.; Halls P. J.; Katritzky A. R. Chem. Ind. 1968, 651.
31. (b) Boulton A. J.; Gripper-Gray A. C.; Katritzky A. R., J. Chem. Soc. B 1967, 911.
32. (c) Aurich H. G.; Weiss W. Chem. Ber. 1973, 106, 2408.
33. (d) Aurich H. G.; Stork K. Chem. Ber. 1975, 108, 2764.
34. (e) Borah H. N.; Boruah R. C.; Sandhu J. S. Heterocycles 1985, 23, 1625.
35. (a) Dormann, E.; Winter, H.; Dyakonow, W.; Gotschy, B.; Lang, A.; Naarmann, H.; Walker, N. Ber. Bunsen-Ges. Phys. Chem. 1992, 96, 922.
36. (b) Kuhn, R., II; Trischmann, H. Monatsh. Chem. 1964, 95, 457-479.
37. (a) Teki, Y. Ph.D. Dissertation, Osaka City University, Osaka, Japan, 1985.
38. (b) Teki, Y.; Takui, T.; Yagi, H.; Itoh, K.; Iwamura, H. J. Chem. Phys. 1985, 83, 539.
39. Sato, K. Ph.D. Dissertation, Osaka City University, Osaka, Japan 1994.
40. (a) Osiecki, J. H.; Ullman, E. F. J. Am. Chem. Soc., 1968, 90, 1078.
41. (b) Caneschi, A.; Laugier, J.; Rey, P. J. Chem. Soc., Perkin Trans. 1 1987, 1077.
42. (c) Caneschi, A., Gatteschi, D., Rey, P. Prog. Inorg. Chem. 1991, 39, 391.
43. For DFT methodology used in this work, see: (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
44. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
45. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian Inc.: Pittsburgh, PA, 1998.
46. (a) Coope, J. A. R.; Farmer, J. B.; Gardner, C. L.; McDowell, C. A J. Chem. Phys. 1965, 42, 54.
47. (b) Ferrante, R. F. J. Phys. Chem. 1990, 94, 4, 3502.
48. (c) The dependence of nitrene zfs upon spin density distribution has also been described by Wasseman in ref 10.
49. -1) was attributed to a small amount of the nitrene in a twisted, nonconjugated conformation.
50. The limitations of spectral Curie law analysis for determining ground-state spin multiplicity preference have been detailed, for example, by: Berson, J. A. In The Chemistry of Quinoid Compounds; Patai, S., Rappaport, Z., Eds.; John Wiley and Sons: 1988; Vol. 2, p 462.
51. Shultz, D. A. Polyhedron 2003, 22, 2423.
52. Ovcharenko, V.; Fokin, S.; Rey, P. Mol. Cryst. Liq. Cryst., Sect. A 1999, 334, 109.
53. Liao, Y.; Xie, C.; Lahti, P. M.; Weber, R. T.; Jiang, J.; Barr, D. P. J. Org. Chem. 1999, 64, 5176.
54. Duling, D. R. J. Magn. Reson. 1994, B104, 105.