Isocyanurate anion radicals via electron-initiated cycloaddition of isocyanates

Organic Letters

Volumn 10, Issue 20, 2008, Pages 4521-4524

  Peters, Steven J ^a   Klen, Joseph R ^a   Smart, Nathaniel C ^a  

^a ILLINOIS STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 61349163035     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol801793t     Document Type: Article

References (30)

1. Isocyanurates are planar and considered aromatic with the nitrogen lone pairs contributing to the π system of the ring.
2. (a) Wirpsza, Z. Polyurethanes: Chemistry, Technology and Application; Ellis Horwood: London, 1993.
3. (b) Zitinkina, A. K.; Sibanova, N. A.; Tarakonov, O. G. Russ. Chem. Rev. 1985, 54, 1866.
4. (c) Nicholas, L.; Gmitter, G. R. J. Cell. Plast. 1975, 267.
5. (a) Fisher, J. F.; Meroueh, S. O.; Mobashery, S. Chem. Rev. 2005, 105, 395.
6. (b) Rigby, J. H.; Brouet, J.; Burke, P. J.; Rohach, S.; Sidique, S.; Heeg, M. J. Org. Lett. 2006, 8, 3121-3123.
7. Olkhovyk, O.; Jaroniec, M. J. Am. Chem. Soc. 2005, 127, 60-61.
8. Symons, M. C.; Trousson, P. M. Radiat. Phys. Chem. 1984, 23, 127-135.
9. Ulrich, H. Chemistry and Technology of Isocyanates; John Wiley and Sons: New York, 1996.
10. The g factor was measured using the perylene cation radical in concentrated sulfuric acid as an internal standard. See: (a) Segal, B. G.; Kaplan, M.; Fraenkel, G. K. J. Chem. Phys. 1965, 43, 4191.
11. (b) Allendoerfer. R. D. J. Chem. Phys. 1971, 55, 361.
12. Levin, G.; Jagur-Grodzinski, J.; Szwarc, M. J. Am. Chem. Soc. 1970, 92, 2268-2275.
13. (a) The propionyl chloride was generated from the acid using the procedure from: Brown, H. C. J. Am. Chem. Soc. 1938, 60, 1325-1328.
14. (b) The acid chloride was exposed to NaNi to generate the propionyl azide which was then heated to form the isocyanate.
15. 1H chemical shift assignments are known. See: Tang, J.; Verkade, J. G. J. Org. Chem, 1994, 59, 4931-4938.
16. (b) Duong, H. A.; Cross, M. J.; Louie, J. Org. Lett. 2004, 6, 4679-4681.
17. Ovchinnikova, N. A.; Sinyakov, A. E.; Reznik, A. M.; Sakharov, S. G.; Gorbunova, Yu. E.; Mikhailov, Yu. N.; Kanishcheva, A. S.; Butskii, V. D. Koord. Khim. 2002, 28, 673-677.
18. ·- has calculated spin densities similar to those of 3·-. (13) For a discussion and examples of systems that undergo J-T distortion upon electron addtion, see: (a) Jahn, H. A.; Teller, E. Proc. R. Soc. London Ser. A 1937,161, 220.
19. (b) Horvat, D. A.; Hammons, J. H.; Stevenson, C. D.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 9523-9526.
20. (c) Kurth, T. L.; Brown, E. C.; Hattan, C. M.; Reiter, R. C.; Stevenson, C. D. J. Phys. Chem. A 2002, 106, 478-481.
21. (d) Gerson, F.; Huber, W. Electron Spin Resonance Spectroscopy of Organic Radicals; Wiley-VCH: Weinheim, 2003; p 161.
22. ·- also show that the neutral isocyanurate ring undergoes a boatlike molecular distortion upon electron reduction.
23. Wertz, J. E.; Bolton, J. R. Electron Paramagnetic Resonance; Chapman and Hall: New York, 1986; p 197.
24. (a) Davies, A. G.; Neville, A. G. J. Chem. Perkin Trans. 1992, 2, 163-169.
25. (b) Russell, G. A.; Underwood, G. R. J. Phys. Chem. 1968, 72, 1074-1076.
26. (a) Das. M. R.; Fraenkel, M. R. J. Chem. Phys. 1965, 42, 1350-1360.
27. (b) Stone, E. W.; Maki, A. H. J. Chem. Phys. 1963, 39, 1635-1642.
28. See Supporting Information for a more detailed discussion of spin polarization contribution to ac.
29. (a) Argabright, P. A.; Phillips, B. L.; DePuy, C. H. J. Org. Chem. 1970, 35, 2253-2257.
30. (b) Bloodworth, A. J.; Davies, A. G. J. Chem. Soc. 1965, 6858-6863.