AMINYLOXIDE (NITROXIDE)-XXXI. UNTERSUCHUNG DER SPINDICHTEVERTEILUNG IN VERSCHIEDENEN AMINYLOXID-TYPEN MIT HILFE 17O-MARKIERTER RADIKALE

Article abstract of DOI:10.1016/0040-4020(80)88050-1

17O-Labelled aminyloxides 4 and 7 have been prepared either by direct reaction of the intermediate aminyl radicals 3 and 6 generated by various methods, with 17O-enriched oxygen, or by spin trap reactions performed with 17O-labelled 2-methyl-2-nitrosopropane (8) and 2-methyl-2-nitropropane (13) respectively.Reaction of 17O-labelled tert-butylhydroxylamine with phoagen yielded 11 which was transformed to the radicals 4d and 4f.Using equations (3) and (4) the spin density p^N_NO and p^O_NO was derived for some dialkylaminyloxides (for instance 4c X=CF3) and tert-butylaminyloxides with conjugated groups (4 X=CO-R, COCl, COOR, COONR2, CN).The spin density distribution in these radicals is discussed.An attempt to calculate the spin density in radicals 4 (X=OR, NR2 and SR) with aid of (3) and (4) yields too large values.For this reason we suggest that the aminyloxide group is non-planar in these radicals.