Reactions of functionalized alkyl halides withN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxide salts

Chemistry of the Nitric Oxide-Releasing Diazeniumdiolate (“Nitrosohydroxylamine”) Functional Group and Its Oxygen-Substituted Derivatives

“…115 Alkylation of Cupferron has received particular attention since under some conditions mixtures of products form, 116 while it is also possible to prepare exclusively O 2alkyl derivatives. 117 An interesting recent study 118 verified that O 1 ethanes to produce formals such as 6 119,120 and reaction with chloromethyl methyl ether to form methoxymethyl derivative 7 121 (the thioether also works well). Alkylation may be used to trap the otherwise unstable diazeniumdiolate formed in a Traube-like reaction of NO with vinyl ketones 21 (eq 25).…”

“…An interesting recent study verified that O 1 -alkylation was a side reaction in the preparation of O 2 -alkyl neocupferron derivatives by isolation of the O -alkylnaphthoquinone bisoxime byproduct (eq 24). Other interesting recent variations on the alkylation theme include the use of dihalomethanes to produce formals such as 6 , and reaction with chloromethyl methyl ether to form methoxymethyl derivative 7 (the thioether also works well). Alkylation may be used to trap the otherwise unstable diazeniumdiolate formed in a Traube-like reaction of NO with vinyl ketones 21 (eq 25).…”

The reaction of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with dihalomethanes

“…We have shown previously L2 that reactions of salts of N-(lMlydroxyalkyl)-N'-hydroxydiazene N-oxides (1) with unsubstituted and 13-substituted alkyl halides mostly result in N-(13-hydroxyalkyl)-N'-alkoxydiazene N-oxides (2) and/or O-substituted N-(13-hydroxyalkyl)-Nnitrosohydroxylamines (3). If halogenated derivatives incorporating an atom with an unshared electron pair (O, N) in the a-position are used as alkylating agents, products of their alkylation on the hydroxy group are formed along with compounds 2. z The dependence of the yield of reaction products on the nature of the initial reagents and reaction conditions is complex and cannot be interpreted unequivocally.…”

“…If halogenated derivatives incorporating an atom with an unshared electron pair (O, N) in the a-position are used as alkylating agents, products of their alkylation on the hydroxy group are formed along with compounds 2. z The dependence of the yield of reaction products on the nature of the initial reagents and reaction conditions is complex and cannot be interpreted unequivocally. Nevertheless, in many cases it is possible to direct the reaction towards the preferred formation of alkoxydiazene N-oxides (2). Taking this into consideration, we studied the possibility to obtain the previously unknown methylene-bis[N'-diazene-N-(13-hydroxyalkyl) N-oxidesl (5),…”