Oxidation alkaline permanganate

A stopped-flow examination of the alkaline permanganate oxidation of phenylnitromethane... 

Oxidation of malonic acid by Cr(VI) has been noted briefly by Snethlage and later by Kemp and Waters . The kinetics are simple second-order but the acidity dependence is complex. Heckner et a/. find the alkaline permanganate oxidation of malonic acid (and also of o- and p-toluic acids and of p-toluene-sulphonic acid) to be retarded by added Mn(VI), viz. 

In 1933, Francis (4) measured the rate of the alkaline permanganate oxidation of coal at screen cuts of through 60 on 100 and through 100 on 200 mesh. He found that the rate of reaction was directly proportional to the external area of the different coal samples, thus inferring that there is little internal area available for reaction. In 1936 Cauzelin and Crussard (8) reached the same conclusion in similar experiments. Since 1933 a vast and complicated pore structure of coal has been discovered. However, the discovery of this pore structure does not invalidate the experimental results of Francis as some authors (19) have suggested. 

The configurations of the asymmetric centers of tiliacorine and tiliacorinine were shown by separately feeding only one labeled enantiomer of Al-meth-ylcoclaurine. (S)- and (/ )-iV-methylcoclaurine were incorporated equally into tiliacorine, but the labeled (5) form (22 ) was converted 70 times more readily than the other enantiomer into tiliacorinine. Alkaline permanganate oxidation of the dimethiodides of tiliacorine derived separately from labeled antipodes de-... 

Alkaline permanganate oxidation of phenytoin will result in quantitative yield of benzophenone. 

Pyrazinecarboxylic acid has been obtained by selenious acid oxidation in pyridine of methylpyrazine or aqueous permanganate oxidation of ethylpyrazine, in yields of 64 and 48%, respectively.171,218 It has also been obtained in 70% yield by partial decarboxylation of pyrazine-2,3-dicarboxylic acid on heating in vacuo at 210°.219 Aqueous permanganate oxidation of 2,5-distyrylpyrazine gives the 2,5-dicarboxylic acid.220 Pyrazine-2,5-dicarboxylic acid has also been prepared in 45% yield by direct carboxylation of pyrazine with carbon dioxide at 50 atm pressure at 250° for 3 hours in the presence of a potassium carbonate and calcium fluoride catalyst.221 Pyrazine-tricarboxylic acid (57), obtainable in only very poor yields by oxidation of 2,5-dimethyl-3-ethylpyrazine, is prepared in 87% yield by alkaline permanganate oxidation of 2-(D-arabo)tetrahydroxybutyl-quinoxaline (56).222 Decarboxylation of the tricarboxylic acid by... 

The methyl ester of oxycellulose, produced by alkaline permanganate oxidation of cuprammonium cellulose followed by treatment with diazomethane, has been reacted with protein by the azide method [34]. Acidic oxyce]]uloses are aiso able to react with alcohols and amines, including proteins, to form esters or amide derivatives. 

Alkaline permanganate oxidation is frequently employed. Examples are 2,6-dimethylheptanoic acid (45%) from 3,7-dimethyI-l-octene, w-ethyl-phenylacetic acid (24%) ° from m-ethylallylbenzene, and azelaic acid (36%) ° from ricinoleic acid. 

Degradation of the carbon chain does not always occur. Dichromate oxidation of triisobutylenes gives acids with the same carbon content as the olefins. The keto acid, benzoylformic acid (55%), is made by hot alkaline permanganate oxidation of styrene. ° ... 

The cyclopentapyrazoles (45 R = H, Me) are obtained in 67% and 54% yields, respectively, by benzilic acid rearrangement of the corresponding indazolediones (44). This ring contraction has many analogs in the next section, and may occur during alkaline permanganate oxidations of suitable substrates. For example, oxidation of fuscinic acid dimethyl ether (46) affords (48) and (49), implicating the a-diketone (47) as a common intermediate. ... 

Alkaline permanganate oxidation is a method for charaeterizing humie substances which has been used extensively for structural elucidation. Alkaline permanganate oxidation of humic substances produces various organic compounds, which are determined by gas chromatography-mass spectrometry GS-MS). The yield of degradation products is usually low, and this se- erely limits the utility of the data. 

The distribution pattern of a,w-dicarboxylic acids for lipids resembled those for humic acid and humin (Fig. 3). This fact clearly indicates the common origin for the polymethylene chains in lipids, humic acid, and humin, which means that phytoplankton-derived lipids actively took part in the formation of humic acid and humin. The relative abundance of polymeth-ylene chains in lipids and humic substances was estimated on the assumption that the yield of production of aliphatic acids from polymethylene chains by alkaline permanganate oxidation was the same for these organic fractions. The following estimations resulted 42% (% of the total amount of polymethylene chains in the sediment) for humin, 38% for lipids, 19% for humic acid, and 1% for fulvic acid. 

Djuricic, M., Murphy, R. C., Vitorovic, D., and Biemann, K. (1971). Organic acids obtained by alkaline permanganate oxidation of kerogen from the Green River (Colorado) shale. Geo-chim. Cosmochim. Acta 35, 1201-1207. 

Hansen, E. H. and Schnitzer, M. (1966). The alkaline permanganate oxidation of Danish illuvial organic matter. Soil Sci. Soc. Am. Proc. 30, 745-748. 

Machihara, T. and Ishiwatari, R. (in press). Evaluation of alkaline permanganate oxidation method for the characterization of young kerogen. Org. Geochem. 

Hill and Edwards (34) have determined the absolute configuration of the C-2 position as S by alkaline permanganate oxidation of (—)-A-benzoyl-3-furyl-P-alanine (14) to L-(+)-A-benzoylaspartic acid, using the conditions developed by Reichstein et al. (55) for the oxidation of the furan ring. Compound 14 is the starting material for the synthesis of the (-I-) enantiomer of febrifugine according to Baker et al. 

Direct oxidation of the ketones leads of course to the familiar cleavage between C.8 and C.9, but alkaline permanganate oxidation of N.l-benzoyldihydrocinchotoxine-iV.r-methiodide (XLIII) results in cleavage of the C.9-C.4 bond, with the formation of IV-benzoylhomocincho-loipon (XLIV) (91). 

Controlled alkaline permanganate oxidation of 5,6-epoxy-5,6-dihydro-/3,/8-carotene (70), 5,6,5, 6 -diepoxy-5,6,5, 6 -tetrahydro-/3,/3-carotene (71),... 

ISHIWATARI R., Morinaga S. and Simoneit B. R. T. (1985) Alkaline permanganate oxidation of kerogens from Cretaceous black shales thermally altered by diabase intmsions and laboratory simulations. Geochim. Cosmochim. Acta 49, 1825-1835. 

Pachter and Sued have prepared (80) in 68% yield by POCI3-promoted condensation of 2,3,4,9-tetrahydro-lH-pyrido[3,4-b]indol-l-one with methyl N-methylanthranilate. Catalytic reduction of (80) yields (67). Danieli and Palmisano 54) have found that (67) can be converted into (68) by a variety of oxidants. In particular, Tl(OAc)3 and DDQ give (68) in 85 and 67% yield, respectively. The yield of (68) from alkaline permanganate oxidation of (67) (in acetone at 0° 65% yield) was improved markedly to 91%, by use of dicyclohexyl-18-crown-6 (methylene chloride at room temperature). 

Oxidative degradation of carotenoids has also been performed with the purpose of localizing cis double bonds in the polyene chain (163). Thus controlled alkaline permanganate oxidation to apocarotenals served to identify violeoxanthin as the 9-cis isomer of violaxanthin (32). 

Postemak, on the other hand, applied the alkaline permanganate oxidation to scyllo-myo-inosose (bioinosose) and obtained DL-idaric acid (4 ). This evidence simultaneously establishes the configurations of the inosose, m o-inositol, and scj/Zto-inositol. The only configuration compatible with the recovery of DL-idaric acid from the inosose is ... 

Posternak established the configurations of d- and L-inositol by isolation of mucic acid and of glucaric acid from the products of the cold alkaline permanganate oxidation of L-inositol (81),... 

Sixteen pentahydroxycyclohexanes are predicted on the basis of stereochemical theory. The configuration of d-quercitol was limited to that shown below by nitric acid oxidation to galactaric (mucic) acid (8 ) and by alkaline permanganate oxidation to 3-deoxy-D-galactaric acid (metasaccharinic acid) (83), This same acid was obtained from Z-viburnitol (58), Hence, the arrangement of hydroxyl groups on carbon atoms 2, 5, and 6 of d-quercitol and Z-viburnitol must be the same. Another series of reactions also led to identical compounds from these two deoxyinositols (53), It was found that Acetobacter suboxydans catalyzed the oxidation of Z-viburnitol to a deoxy-... 

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