AMINIUM NITRATES

Aminium iodates and periodates, 36 Aminium nitrates, 36 Aminium perchlorates, 36 Aminomethoxy compounds, 36 Amminechromium peroxocomplexes, 37 Amminemetal azides, 37 Amminemetal halides, 38 Amminemetal nitrates, 38 Amminemetal oxosalts, 38 Annulenes, 43 Aprotic solvents, 43 Aqua regia, 43... 

The success of this transformation depends upon the oxidation potential of the ESE group (Eox 1.5 V), which is lower than that of the alkyl silyl ether group (Eax 2.5 V). Recently, Schmittel et al.35 showed (by product studies) that the enol derivatives of sterically hindered ketones (e.g., 2,2-dimesityl-1-phenyletha-none) can indeed be readily oxidized to the corresponding cation radicals, radicals and a-carbonyl cations either chemically with standard one-electron oxidants (such as tris(/>-bromophenyl)aminium hexachloroantimonate or ceric ammonium nitrate) or electrochemically (equation 10). 

Reagents for amination, nitrosation and nitration of tertiary alkylamines are discussed in the appropriate reviews listed in Sections 6.1.3.1.4 and 6.I.3.I.5. Tertiary amines can be nitrosated with dealkylation by dinitrogen tetroxide for example, 1-methylpiperidine gave 1-nitrosopiperidine (80%). lliis reaction probably starts by one-electron oxidation of the amine, the aminium ion then undergoing dealkylation. Other oxidative d ylations and dealkylations include the formation of iV-nitrosodibenzylamine in high yield from the acid chloride (PhCH2)2NCOCl and sodium nitrite and the conversion of the amine (43) into the nitramine (44) with nitric acid. ... 

Protonated A-nitroso amines undergo photolytic decomposition from the excited state generating transient aminium radicals and nitric oxide. Aminium radicals, which are electrophilic radicals, initiate the addition to alkenes to give //-amino nitroso compounds or oc-amino oximes (Section 7.2.5.2), however, under an oxygen atmosphere, //-nitryloxy amines (/i-amino nitrates) are produced through peroxynitrites intermediates97-99. 

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