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New 2‐substituted pyrroline‐ N ‐oxides: An EPR solvent study of the radical spin adducts
Author(s) -
Janzen Edward G.,
Zhang YongKang,
Haire D. Lawrence
Publication year - 1994
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1260321203
Subject(s) - pyrroline , chemistry , adduct , oxide , nitrone , electron paramagnetic resonance , solvent , medicinal chemistry , organic chemistry , catalysis , nuclear magnetic resonance , cycloaddition , physics
Ten substituted 5,5‐dimethyl‐1‐pyrroline‐ N ‐oxides as well as the parent nitrene spin trap (DMPO) were prepared: 5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide, 2,5,5‐trimethyl‐1‐pyrroline‐ N ‐oxide, 2‐ tert ‐butyl‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide, 2‐phenyl‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide, 2‐ d 5 ‐phenyl‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide, 2‐phenyl‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide‐ nitronyl ‐ 13 C, 2‐(4‐fluorophenyl)‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide, 2‐(4‐chlorophenyl)‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide, 2‐(4‐ tert ‐butylphenyl)‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide, 2‐(4‐methylphenyl‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide) and 2‐(2‐ methylphenyl)‐5,5‐dimethyl‐1‐pyrroline‐ N ‐oxide. Analytical (i.e. EPR‐grade) samples of these novel cyclic nitrones were obtained and characterized by (among other methods) 1 H NMR spectroscopy. Reduction of DMPO and these various 2‐substituted cyclic nitrones gave the corresponding cyclic N,N ‐dialkylhydroxylamines, whose structures and conformations were also analyzed by 1 H NMR spectroscopy. Air oxidation of these cyclic N,N ‐dialkylhydroxylamines provided access to the EPR spectra of the hydrogen, methyl, tert ‐butyl, phenyl, d 5 ‐phenyl, nitronyl ‐ 13 C‐phenyl, 4‐fluorophenyl, 4‐chlorophenyl, 4‐ tert ‐butylphenyl, 4‐methylphenyl and 2‐methylphenyl cyclic aminoxyl (pyrrolidine N ‐oxyl nitroxide) radical spin adducts of DMPO. The 14 N, 13 C (where applicable) and 1 H hyperfine splitting constants of these aminoxyl adducts in ten solvents of widely different polarities (e.g., hexane to water) were measured and the solvent effect on these parameters was evaluated. It was found that for the various 2‐substituted DMPO‐type spin adducts both the nitrogen and β‐hydrogen EPR hyperfine splittings correlated linearly ( r 2 ⩾ 0.90) with typical solvent polarity parameters such as E T (30). The correlation between the nitrogen and β‐hydrogen hyperfine splitting constants were even more linear ( r 2 ⩾ 0.97).