With potassium permanganate

By oxidation of aldehydes with potassium permanganate solution, for example ... 

Saccharin (imide of o-sulphobenzoic acid). Upon oxidising o toluene-sulphonamide with potassium permanganate in alkaline solution, the sodium salt of o-sulphonamidobenzoic acid is formed, which upon acidifying with concentrated hydrochloric acid or warming passes spontaneously into the cyclic imide of o-sulphobenzoic acid or saccharin ... 

Nicotinic acid is prepared in good tdeld by the oxidation of p picollne with potassium permanganate ... 

Perfluoroepoxides have also been prepared by anodic oxidation of fluoroalkenes (39), the low temperature oxidation of fluoroalkenes with potassium permanganate (40), by addition of difluorocarbene to perfluoroacetyl fluoride (41) or hexafluoroacetone (42), epoxidation of fluoroalkenes with oxygen difluoride (43) or peracids (44), the photolysis of substituted l,3-dioxolan-4-ones (45), and the thermal rearrangement of perfluorodioxoles (46). 

Oxidation. Nitroparaffins are resistant to oxidation. At ordinary temperatures, they are attacked only very slowly by strong oxidi2ing agents such as potassium permanganate, manganese dioxide, or lead peroxide. Nitronate salts, however, are oxidi2ed more easily. The salt of 2-nitropropane is converted to 2,3-dimethyl-2,3-dinitrobutane [3964-18-9], acetone, and nitrite ion by persulfates or electrolytic oxidation. With potassium permanganate, only acetone is recovered. 

Quantitative Analysis. OxaUc acid is precipitated as calcium oxalate from a solution containing oxaUc acid, and the calcium oxalate obtained is then weighed. If there are no organic substances other than oxaUc acid present, oxaUc acid can be titrated quantitatively with potassium permanganate. 

Manufacture. The only current U.S. manufacturer of trimesic acid is Amoco Chemical Co. It is produced by oxidation of mesitylene (1,3,5-trimethylbenzene) via the Hquid-phase oxidation in acetic acid using the cobalt— manganese—bromine catalyst system (138). This is a variant of the system used to produce terephthaUc and isophthaUc acids as well as trimellitic anhydride. American Bio-Synthetics Corp. did produce it by batch oxidation of mesitylene with potassium permanganate. 

Various methods can be used to analy2e succinic acid and succinic anhydride, depending on the characteristics of the material. Methods generally used to control specifications of pure products include acidimetric titration for total acidity or purity comparison with Pt—Co standard calibrated solutions for color oxidation with potassium permanganate for unsaturated compounds subtracting from the total acidity the anhydride content measured by titration with morpholine for content of free acid in the anhydride atomic absorption or plasma spectroscopy for metals titration with AgNO or BaCl2 for chlorides and sulfates, respectively and comparison of the color of the sulfide solution of the metals with that of a solution with a known Pb content for heavy metals. 

The oxidation of teUurium(IV) by permanganate as an analytical method has been studied in some detail (26). The sample is dissolved in 1 1 nitric-sulfuric acid mixture addition of potassium bisulfate and repeated fuming with sulfuric acid volatilises the selenium. The tellurite is dissolved in 10 vol % sulfuric acid, followed by threefold dilution with water and titration with potassium permanganate ... 

The long-standing manufacturing route to 2-thiopheneacetic acid [1918-77-0] has also involved 2-acetylthiophene. Oxidation with potassium permanganate under controlled conditions leads to 2-thiopheneglyoxyhc acid [4075-59-6], which maybe isolated as ammonium salt. The salt is then carried... 

Methods of Purification. Although carbon dioxide produced and recovered by the methods outlined above has a high purity, it may contain traces of hydrogen sulfide and sulfur dioxide, which cause a slight odor or taste. The fermentation gas recovery processes include a purification stage, but carbon dioxide recovered by other methods must be further purified before it is acceptable for beverage, dry ice, or other uses. The most commonly used purification methods are treatments with potassium permanganate, potassium dichromate, or active carbon. 

Potassium Permanganate. Probably the most widely used process for removing traces of hydrogen sulfide from carbon dioxide is to scmb the gas with an aqueous solution saturated with potassium permanganate [7722-64-7]. Sodium carbonate is added to the solution as buffer. The reaction is as foUows ... 

Since the pyridazine ring is generally more stable to oxidation than a benzene ring, oxidation of alkyl and aryl substituted cinnolines and phthalazines can be used for the preparation of pyridazinedicarboxylic acids. For example, oxidation of 4-phenylcinnoline with potassium permanganate yields 5-phenylpyridazine-3,4-dicarboxylic acid, while alkyl substituted phthalazines give pyridazine-4,5-dicarboxylic acids under essentially the same reaction conditions. 

Pyridazine aldehydes and ketones with the carbonyl group at the ring or in a side chain react in the usual manner. They form hydrazones, semicarbazides, oximes, etc. Side-chain aldehydes can be easily oxidized to pyridazinecarboxylic acids with silver nitrate and side-chain ketones are oxidized to carboxylic acids by treatment with potassium permanganate or hydrogen peroxide. 

Methyl groups in pyridopyrazines (64IMC240) and pyridopyrazinones (71TH21500) are oxidized to carboxylic acids with potassium permanganate. Aryl carbinol substituents are also very readily oxidized to benzoyl derivatives in alkaline conditions (76CPB238). Bromina-tion of 2,3-dimethylpyrido[3,4-f ]pyridazine gives the 2,3-bisbromomethyl derivative, whilst... 

The stability of various heterocycles can be also compared using oxidation procedures. Thus, the oxidation of the heterocycles in Scheme 29 with potassium permanganate showed that under these reaction conditions the isoxazole ring is more stable than the furan ring but less stable than the pyrazole and furazan rings. 

This material is contaminated with -10% of 3-methylcyclohexenone. Material of greater purity can be obtained by extending the time of irradiation, by carrying out an efficient distillation of product, or by decomposing starting material with potassium permanganate prior to distillation. 

Butyroin has been prepared by reductive condensation of ethyl butyrate with sodium in xylene, or with sodium in the presence of chloro-trimethylsilane. and by reduction of 4,5-octanedlone with sodium l-benzyl-3-carbamoyl-l,4-dihydropyridine-4-sulfinate in the presence of magnesium chloride or with thiophenol in the presence of iron polyphthalocyanine as electron transfer agent.This acyloin has also been obtained by oxidation of (E)-4-octene with potassium permanganate and by reaction of... 

Ketones are more stable to oxidation than aldehydes and can be purified from oxidisable impurities by refluxing with potassium permanganate until the colour persists, followed by shaking with sodium carbonate (to remove acidic impurities) and distilling. Traces of water can be removed with type 4A Linde molecular sieves. Ketones which are solids can be purified by crystallisation from alcohol, toluene, or petroleum ether, and are usually sufficiently volatile for sublimation in vacuum. Ketones can be further purified via their bisulfite, semicarbazone or oxime derivatives (vide supra). The bisulfite addition compounds are formed only by aldehydes and methyl ketones but they are readily hydrolysed in dilute acid or alkali. 

The inadequacy of these formulae became evident when the oxidation of tropine was studied. With potassium permanganate, in presence of acid, or with chromic acid, tropine and tropidine give rise to a series of oxidation products, the interrelationships of which are shown in the scheme on p. 75. 

Codeinone, CjaHijOgN. This ketone (XLVII) corresponds to the secondary alcohol codeine and its stereoisomeride wocodeine. It may be prepared by oxidising codeine with potassium permanganate in acetone or with potassium dichromate in dilute sulphuric acid and in various other ways. Codeinone can be reduced to codeine electrolytically or by chemical methods. It crystallises from alcohol in prisms, m.p. 185-6, [a]J, ° — 205° (EtOH). The hydrochloride, B. HCl. HjO, has m.p. 179-80°, picrate, m.p. 205°, methiodide, B. CHjI. 2H2O, m.p. 180°. 

The alkaloid contains two methoxyl groups, and is demethylated by hydriodic acid to berberoline, CigHj304N (amorphous). When berberine is oxidised in warm alkaline solution with potassium permanganate a series of degradation products is obtained, of which the following are the more important. 

---