Potassium permanganate carbonyl compounds

Tris(dimethylamino)sulfonium difluo-rotrimethylsilicate, 336 Xenon(II) fluoride, 345 Alkyl bromides Potassium permanganate, 258 Sodium bromide, 46 Tetraethylammonium bromide, 46 Alkyl iodides Aluminum iodide, 17 Potassium permanganate, 258 Sodium iodide, 46 Tetraethylammonium iodide, 46 Alkynes (see also Acetylenic carbonyl compounds, Diynes, Enynes, Propar-gyl alcohols)... 

Oxidation with potassium permanganate of the nitronate salts to yield carbonyl compounds has been discussed in Section 5.7.7, p. 599 the method is very suitable for the preparation of ketones from secondary nitroalkanes and the experimental details may be readily adapted from Expt 5.84. 

Sodium periodate (sodium metaperiodate), NaI04 (mp 300 °C dec), which is commercially available, is applied mainly in aqueous or aqueous-alcoholic solutions. Like the free periodic acid, sodium periodate cleaves vicinal diols to carbonyl compounds [762], This reaction is especially useful in connection with potassium permanganate [763, 764] or osmium tetroxide [765], Such mixed oxidants oxidize alkenes to carbonyl compounds or carboxylic acids, evidently by way of vicinal diols as intermediates. Sulfides are transformed by sodium periodate into sulfoxides [322, 323, 766, 767, 768, 769, 770, 771, 772], and selenides are converted into selenoxides [773]. Sodium periodate is also a reoxidant of lower valency ruthenium in oxidations with ruthenium tetroxide [567, 774],... 

Barium manganate, BaMn04, is commercially available. The dark-blue crystals are obtained from aqueous solutions of barium chloride and potassium permanganate [552, 555]. It oxidizes alcohols, especially benzylic alcohols, to carbonyl compounds [552, 555] hydroquinone to quinone [555] benzylamines to benzaldehydes [555] aromatic amines to azo compounds [555] and phosphines to phosphine oxides [555],... 

The results of some oxidations with potassium permanganate differ depending on the pH of the reaction. For example, stearolic acid gives 9,10-diketostearic acid at pH 7-7.5 (achieved with carbon dioxide) and azelaic acid on treatment at pH 12 [864]. In some reactions, potassium permanganate is used as a catalyst for oxidation with other oxidants, such as sodium periodate. Thus alkenes are cleaved to carbonyl compounds or acids via vicinal diols obtained by hydroxylation with potassium permanganate, followed by cleavage by sodium periodate [763, 552]. 

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]. 

Diols are oxidatively cleaved by reaction with periodic acid (HIO4) to yield carbonyl compounds, a reaction similar to the KMnO cleavage of aJkenes just discussed. The sequence of (1) alkene hydroxylation with OsO< j followed by (2) diol cleavage with HIO4 is often an excellent alternative to direct alkene cleavage with ozone or potassium permanganate. 

Kumar A, Jain N, Chauhan SMS (2004) Oxidation of benzylic alcohols to carbonyl compounds with potassium permanganate in ionic liquids. Synth Commun 34 2835-2842... 

Diols can be oxidised further to form carbonyl compounds. This results in the cleavage of the C-C bond. When potassium permanganate is reacted with alkenes at room temperature or above, the intermediate 1,2-diol can be further oxidised to form carboxylic acids. 

Compounds of formula 63 are readily cyclized by reduction of the nitro group with Raney nickel and hydrogen. The amine thus formed condenses intramolecularly, with the carbonyl function providing the 3,4-dihydro system 64. This may be smoothly oxidized with iodine or an acetone solution of potassium permanganate. " " This route has been used for the unambiguous synthesis of compounds 65, 66, 67, and 68 48.49 Qf particular interest are compounds 66 and 67, which have been used to confirm the orientation of products from the reaction of polyaminopyridines with pyruvaldehyde and p-chlorophenylglyoxal. ... 

Some chemical processes require the use of hazardous materials or heavy metals. Oxidations of alcohols into carbonyl compounds or carboxylic acids were frequently performed using either chromic acid or potassium permanganate. However, these two oxidants are derived from heavy metals, which are toxic and hence environmentally hazardous. Safe disposal of salts of these metals thus presents a considerable environmental concern. Fortunately, hypohalites may also be used to oxidize alcohols into carbonyl compounds and carboxylic acids, as exemplified in the procedures in Section 16.2.This oxidation procedure exemplifies green chemistry because the hypohalites are reduced to water and halide ion, which has little environmental impact. 

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