Über Nitrosoverbindungen, XIII

Abstract

Die sek. und tert. 7V-Nitroso-A-dekalyl-hydroxylamine lassen sich aus den zugehörigen iV-Dekalylhydroxylaminen durch Nitrosierung bei tiefer Temperatur herstellen. Eine photochemische Synthese einiger dieser Stoffe ist ebenfalls möglich.Die TV-Nitroso-hydroxylamin-Verbindungen sind teilweise sehr unbeständig und zerfallen unter Abspaltung nitroser Gase in die entsprechenden Bis-nitroso-dekaline, Nitroverbindungen und Oktaline.A. Darstellung und Eigenschaften der TV-Nitroso-TV-dekalyl-hydroxylamineWie bereits früher beobachtet2, bilden sich bei der Photooximierung des Dekalins nach unserem älteren Verfahren u. a. auch /V-Nitrosoverbindungen. Die zur Identifizierung dieser Produkte notwendigen A^-Nitroso-Ar-dekaIyl-hydroxylamine wurden von uns aus den entsprechenden Hydroxylaminen oder vor teilhafter aus deren Hydrochloriden durch U m setzung m it Nitrit hergestellt3-5.Die als Ausgangsstoffe dienenden A^-Dekalylhydroxylamine sind teilweise noch nicht beschrieben. Ihre Darstellung wird im experimentellen Teil ange geben.

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

“…An important recurring theme in the reactions of nitric oxide which will be described in more detail later is the radical addition of two molecules of NO across the nitrogen−oxygen double bond of nitroso compounds to produce O 1 -nitrosodiazeniumdiolates (for example, the intermediate in eq 13) which are highly unstable and can produce a variety of products. If the reaction is conducted in the cold, C -diazeniumdiolates may be produced as their alkylammonium salts (eq 13), copper complexes, sodium salts, or protonated forms . When the NO supply is not in large excess, the intermediate radical formed via addition of a single NO to the nitrogen ultimately generates a product that can be detected by ESR, and this forms the basis of a spin-trapping experiment used in biomedical research. , A similar mechanism probably governs the production of diazeniumdiolates from the reaction of NO with radicals generated from organic peroxides in the presence of iron sulfate as shown in eq 14 .…”

“…If the reaction is conducted in the cold, Cdiazeniumdiolates may be produced as their alkylammonium salts 72 (eq 13), copper complexes, 72 sodium salts, 73 or protonated forms. 74 When the NO supply is not in large excess, the intermediate radical formed via addition of a single NO to the nitrogen ultimately generates a product that can be detected by ESR, and this forms the basis of a spin-trapping experiment used in biomedical research. 75,76 A similar mechanism probably governs the production of diazeniumdiolates from the reaction of NO with radicals generated from organic peroxides in the presence of iron sulfate as shown in eq 14.…”