Oxidation to nitro compounds

Nitroso compounds are oxidized to nitro compounds by hydrogen peroxide and dinitragen tetroxide [S2] (equation 74)... 

Aiiphadc md aromadc primary amines are rapidly md efficiently oxidized to nitro compounds by dimethyldioxirime. Dimethyldioxirime is prepared by teacdon of OXONE (Du-... 

Tertiary alkyl primary amines can be oxidized to nitro compounds in excellent yields A ith KMn04. This type of nitro compound is not easily prepared in other ways. 

All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyl dioxirane." Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone, various peroxyacids," MeRe03/H202,"" Oxone ," ° tcrt-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds, and sodium perborate." ... 

Dimethyl dioxirane in wet acetone oxidizes isocyanates to nitro compounds (RNCO —> RN02). Oximes can be oxidized to nitro compounds with peroxytri-fluoroacetic acid, or Oxone ," sodiumperborate," among other ways. " Primary and secondary alkyl azides have been converted to nitro compounds by treatment with PhjP followed by ozone. Aromatic nitroso compounds are easily oxidized to nitro compounds by many oxidizing agents. ... 

Aliphatic and aromatic primary amines are rapidly and efficiently oxidized to nitro compounds by dimethyldioxirane.111 Dimethyldioxirane is prepared by reaction of OXONE (DuPont trademark)-2KHS05-KHS04-K2S04 with buffered aqueous acetone.112... 

The popularity of the Nef reaction is due in part to the ready availability of nitro compounds. Primary and secondary halides react with sodium nitrite in dimeAyl sulfoxide (DMSO) or dimethylform-amide (DMF) to give useful yields of nitro compounds. Primary amines can be oxidized to nitro compounds with potassium permanganate, m-chloroperbenzoic acitP or ozone. Chlorination of oximes with hypochlorous acid and reduction with magnesium, zinc or hydrogen/lpalladium gives secondary nitro compounds. Stabilized carbanions can be nitrated by treauitent with a nitrate ester, and enol acetates are nitrated by acetyl nitrate to give nitro ketones. ... 

The spectrum of applications of potassium permanganate is very broad. This reagent is used for dehydrogenative coupling [570], hydrox-ylates tertiary carbons to form hydroxy compounds [550,831], hydroxylates double bonds to form vicinal diols [707, 296, 555, 577], oxidizes alkenes to a-diketones [560, 567], cleaves double bonds to form carbonyl compounds [840, 842, 552] or carboxylic acids [765, 841, 843, 845, 852, 869, 872, 873, 874], and converts acetylenes into dicarbonyl compounds [848, 856, 864] or carboxylic acids [843, 864], Aromatic rings are degraded to carboxylic acids [575, 576], and side chains in aromatic compounds are oxidized to ketones [566, 577] or carboxylic acids [503, 878, 879, 880, 881, 882, 555]. Primary alcohols [884] and aldehydes [749, 868, 555] are converted into carboxylic acids, secondary alcohols into ketones [749, 839, 844, 863, 865, 886, 887], ketones into keto acids [555, 559, 590] or acids [559, 597], ethers into esters [555], and amines into amides [854, 555] or imines [557], Aromatic amines are oxidized to nitro compounds [755, 559, 592], aliphatic nitro compounds to ketones [562, 567], sulfides to sulfones [846], selenides to selenones [525], and iodo compounds to iodoso compounds [595]. 

Oximes are either oxidized to nitro compounds [823] or converted into their respective parent ketones [422, 427, 527, 660]. Oxidation to the parent ketones applies also to semicarbazones 427, 527], dimethylhydrazones [528, 529], tosylhydrazones [527, 528, 529], phenylhydrazones [527], p-nitrophenylhydrazones [527], and 2,4-dinitrophenylhydrazones [527] (equations 454-456). 

Primary aromatic amines are oxidized to nitro compounds by peroxy adds perboric acid [194], peroxysulfuric acid [203], peroxyacetic acid [253],... 

I crmaleic acid can be used in the Baeyer-Villiger reaction, as illustrated for the case of cyclooctanone. It epoxidizes terminal olehns eflSciently at a low temperature l -oclene affords the epoxide in 80% yield at 0° but at 25° the yield is only 40%. In I he case of the more reactive internal olefins the epoxide ring is cleaved even at 0° to give the diol monomaleate. Aromatic amines with electron-withdrawing substituents MIC oxidized to nitro compounds. 

The amino groups of amino esters (54) [37] and azides (56) [38] are also substrates for easy oxidation to nitro compounds. Baeyer-Villiger oxidation of ketones (58) proceeds at 0°C over 4 h to give a mixture of esters (60) and (61) via a dioxirane intermediate, intermediacy of which was proposed on the basis of the complete scrambling of the ester oxygen with heavy oxygen in H18OF [39] (Scheme 2.50). 

Whereas peroxyacetic acid oxidizes aromatic amines at room temperature to nitroso compounds, further oxidation to nitro compounds occurs in boiling chloroform.207 Trifluoroperoxyacetic acid208 and a mixture of maleic anhydride and hydrogen peroxide209 are valuable reagents for oxidizing aromatic amines in general to nitro compounds. 

Primary amines are oxidized to hydroxlyamines, which in turn are oxidized to ni-troso compounds, which are oxidized to nitro compounds. Hydrogen peroxide, peroxy-acids, and other common oxidizing agents are used to oxidize amines. The oxidation reactions generally take place by mechanisms that involve radicals, so they are not well characterized. 

Oxidation of amines Primary amines are oxidized to nitro compounds, secondary amines to hydroxylamines, and tertiary amines to amine oxides (Section 21.7). 

Primary amines are readily oxidized to nitro compounds in high... 

Anilines containing a carboxylic or alcoholic functionality are oxidized to nitro compounds by oxone in 20-50% aqueous acetone at 18 C in 73-84% yields [46]. When the reactions are performed in the absence of acetone, lower yields are obtained, suggesting the generation of dimethyldioxirane, which competes with oxone. 

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