Abstract
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 phosgen yielded 11 which was transformed to the radicals 4d and 4f. Using equations (3) and (4) the spin density ϱ N NO and ϱ O NO was derived for some dialkylaminyloxides (for instance 4c XCF 3) and tert-butylaminyloxides with conjugated groups (4 XCO-R, COCl, COOR, COONR 2, CN). The spin density distribution in these radicals is discussed. An attempt to calculate the spin density in radicals 4 (XOR, NR 2 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.
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