Aromatische Diazoniumsalze, VI; Nitroso‐acyl‐amine und Diazoester, XIV Eine neue Reaktionsweise des N ‐Nitrosoacetanilids

Abstract

Eine friiher beschriebene6) Nebenreaktion beim Zerfall des N-Nitrosoacetanilids in Athanol/ Kaliumacetat, die zur Bildung eines Salzes K[C8H8N303] fuhrte, wurde erneut untersucht. Es ist wahrscheinlich, daD diese Verbindung durch radikalische Addition von N O an die Nitrosogruppe des N-Nitrosoacetanilids und anschlieDende Reduktion entsteht. Das Kaliumsalz und ein entsprechendes Silbersalz werden in fjbereinstimmung mit spektroskopischen Daten als Salze des N-Nitroso-N-(N-phenylacetamido)hydroxylamins (7) formuliert. Die NMR-Linienformanalyse gestattet die Messung einer Rotationsschwelle mit AGf = 16.0 und AGO = 0.6 kcal/mol. Aromatic Diazonium Salts, VI"; Nitrosoacylamines and Diazoesters. XIV'' A New Reaction Mode of N-NitrosoacetanilideA side reaction in the decomposition of N-nitrosoacetanilide in ethanol/potassium acetate, which has been described to produce a salt K[C8H8N3O3l6), was reinvestigated. It is probable that this compound is formed by a free radical addition of NO to the nitroso group of N-nitrosoacetanilide and subsequent reduction. The potassium salt and the corresponding silver salt are considered to be derived from N-nitroso-N-(N-pheny1acetamido)hydroxylamine (7) in agreement with spectroscopic data. Dynamic n. m. r. allows to measure a rotation process with AGf = 16.0 and AG" = 0.6 kcal/mole. N-Nitrosoacetanilid (1) hat seit seiner erstmaligen Herstellung im Jahre 1876 bis zum heutigen Tag durch die Vielfalt seiner Reaktivitat zahlreiche Untersuchungen angeregt 3* ' ).

Direct Reaction of Amides with Nitric Oxide To Form Diazeniumdiolates

“…The only product of such a hypothetical reaction that we could locate had the constitution of N-diazeniumdiolated acetanilide ion, but it was reportedly generated in a radical-mediated side reaction in the decomposition of N-nitrosoacetanilide. 14 (Several Ndiazeniumdiolated carbamates have also been prepared by routes that bypassed the ionic structure 1 by first O-alkylating the terminal oxygen of IPA/NO to make a neutral species and then acylating the NH group.) 15,16 Mechanistically, by analogy with the pathways established for the primary amine diazeniumdolates, we assume that the decomposition of ions 1 consists of two general mechanisms, one being a major, or in the case of 1a exclusive, pathway leading to regeneration of the two NO molecules, with the starting amide being the organic product.…”

“…We were surprised to find no prior literature documenting a successful reaction of NO directly with an amide. The only product of such a hypothetical reaction that we could locate had the constitution of N -diazeniumdiolated acetanilide ion, but it was reportedly generated in a radical-mediated side reaction in the decomposition of N -nitrosoacetanilide . (Several N -diazeniumdiolated carbamates have also been prepared by routes that bypassed the ionic structure 1 by first O -alkylating the terminal oxygen of IPA/NO to make a neutral species and then acylating the NH group.…”