Filemon
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nitro from amine
Is it possible to oxidize an amine to nitro with peracetic acid?
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solo
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Reference Information
The Synthesis of Nitro and Dimeric Nitroso Sugars by Peracid Oxidation of Amino Sugars
Hans H. Baer and Shuet-Hing Lee Chiu
Can. J. Chem./Rev. can. chim. 51(11): 1812-1818 (1973)
Abstract
A number of methyl 3-amino-3-deoxyaldopyranosides were oxidized with m-chloroperbenzoic acid. The reaction, which had been previously applied to
steroidal amines (6), has provided a new route to nitro sugars
and at the same time furnished hitherto unknown nitroso sugar derivatives, namely, dimeric methyl 3- deoxy-3-nitrosoaldopyranosides. Oxidation of a
model compound, iratzs-2-aminocyclohexanol, likewise
gave the corresponding nitro and dimeric nitroso alcohols. The combined yields of oxidation products ranged from 40 to 95%.
Attachment: The Synthesis of Nitro and Dimeric Nitroso Sugars by Peracid Oxidation of Amino Sugars.pdf (431kB)
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Sergei_Eisenstein
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| Quote: | | Is it possible to oxidize an amine to nitro with peracetic acid? |
As far as my theoretical knowledge on the subject reaches, amines are oxidized to amine N-oxides by peroxides, e.g. triethylamine is oxidized to
triethyl amine N-oxide.
damnant quod non intelligunt
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Nicodem
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Only certain primary amines can be oxidized to nitro compounds, but with peracetic acid not really. Generally you need more electrophilic oxygen
introducing reagents. DMDO (dimethyldioxirane) formed in situ from Oxone™ in acetone is reported to work well for anilines (forming nitrobenzenes)
and t-butylamines but not really well (actually, not at all in most cases) on other amines. With t-butylamine itself even KMnO4
works well in its oxidation to t-BuNO<sub>2</sub>. The complication with other primary amines is the deviation of the reaction to
the expected C-oxidation route (R<sub>2</sub>CH-NH<sub>2</sub> => R<sub>2</sub>C=O; and so on...).
Secondary amines give N,N-dialkylhydroxylamines or aminoxyls by oxidation with some peracids.
Tertiary amines give N-oxides like Sergei already said.
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