Oxidation of N,N'-Dialkyl-1,2-bishydroxylamines

Article abstract of DOI:10.1021/jo00199a042

Oxidation of N,N'-dialkyl-1,2-bishydroxylamines RNHOCH2CH2ONHR gives products that are a function of oxidant.For R = i-Pr (5) and m-chloroperbenzoic acid the products are diisopropyl azo dioxide, HOCH2CH2ONHCH(CH3)2, and ethylene glycol.Product ratios indicate independent oxidation of the two hydroxylamine functions.Na2WO4/H2O2 in D2O gives the azo dioxide, ethylene glycol, and acetone oxime.Oxidation with bromine and 1,4-diazabicyclo<2.2.2>octane or tert-butyl hypochlorite and triethylamine gives product ratios that are consistent with two pathways to the bis oxime 7: one that appears to give 7 directly and a second that goes through the monohydroxylamine monooxime 15.It is proposed that the former reaction proceeds through the 1,4,2,3-dioxadiazine ring, which is oxidized quickly to products.Reaction products from the bishydroxylamine with R = CH3 are similar to those with R = i-Pr.