Formation of aminoxyls by oxidative addition of N-tert-butylhydroxylamine to acceptor olefins

Abstract

The reaction between an acceptor olefin (symbolized as C[double bond, length half m-dash]C and substituted by at least one conjugatively electron-withdrawing group) and N-tert-butylhydroxylamine in the presence of t-BuNO as an oxidant gives an aminoxyl which formally is a spin adduct of HC–C˙ and t-BuNO and in the appropriate cases identical to the aminoxyl formed in the thermal or photochemical reaction between C[double bond, length half m-dash]C and α-phenyl-N-tert-butylnitrone (PBN). The acceptor olefins studied were N-phenylmaleimide, maleimide, N-methylmaleimide, maleic anhydride, diethyl fumarate, diethyl 2,3-(²H₂)fumarate, diethyl maleate, trimethyl ethylenetricarboxylate, 1,4-benzoquinone, fumaronitrile, methyl acrylate, methyl methacrylate and acrylonitrile.

References

1. L. Eberson and O. Persson, Acta Chem. Scand., 1998, 52, 1081.
2. T. Sato, M. Abe and T. Otsu, J. Macromol. Sci., Chem., 1981, A15, 367.
3. (a) E. A. Mash, H.-G. Korth and S. M. DeMoss, Tetrahedron, 1997, 53, 15297; (b) C. Chatgilialoglu and K. U. Ingold, J. Am. Chem. Soc., 1981, 103, 4833.
4. D. Niu and K. Zhao, J. Am. Chem. Soc., 1999, 121, 2456 and references cited therein.
5. For reviews, see H. G. Aurich, in Nitrones, nitronates and nitroxides, Wiley, New York, 1989, Chaps. 4 and 5.
6. M. Lucarini, G. F. Pedulli, A. Alberti, C. Paradisi and S. Roffia, J. Chem. Soc., Perkin Trans. 2, 1993, 2083.
7. L. Eberson, O. Persson, H. K. Hall, Jr., A. B. Padias and P. Steel, Macromolecules, to be submitted.
8. For a review, see S. Rádl, Adv. Heterocycl. Chem., 1996, 67, 199.
9. For a review, see C. J. Hawker, Acc. Chem. Res., 1997, 30, 373.
10. D. Duling, Public EPR Software Tools, National Institute of Environmental Health Sciences, 1996.