Permanganate oxidant

Out first example is 2-hydroxy-2-methyl-3-octanone. 3-Octanone can be purchased, but it would be difficult to differentiate the two activated methylene groups in alkylation and oxidation reactions. Usual syntheses of acyloins are based upon addition of terminal alkynes to ketones (disconnection 1 see p. 52). For syntheses of unsymmetrical 1,2-difunctional compounds it is often advisable to look also for reactive starting materials, which do already contain the right substitution pattern. In the present case it turns out that 3-hydroxy-3-methyl-2-butanone is an inexpensive commercial product. This molecule dictates disconnection 3. Another practical synthesis starts with acetone cyanohydrin and pentylmagnesium bromide (disconnection 2). Many 1,2-difunctional compounds are accessible via oxidation of C—C multiple bonds. In this case the target molecule may be obtained by simple permanganate oxidation of 2-methyl-2-octene, which may be synthesized by Wittig reaction (disconnection 1). 

The intermediate formed in the oxidation of alkenes by permanganate ion is considered a cycHc manganate(V) ester (92). Investigations have suggested that manganate(V) intermediates play a significant role in virtually all permanganate oxidation reactions. It is therefore the further reactions of the... 

Additionally, the enthalpies of activation (142) for the permanganate oxidation of organic compounds is characteristically low in the range of... 

The close chemical relationship among these stmctural entities, as well as the uniqueness of (1) and (2), have been evident from the time of the earhest stmctural studies. Permanganate oxidation of (1) (2) produces 2,3-pyridinedicarboxyhc acid (quinolinic acid [89-00-9]) (3), whereas similar treatment of (2) (3) yields a mixture of 3,4-pyridinedicarboxyhc acid (cinchomeronic acid [490-11 -9]) (4) and phthaUc acid. 

Potassium permanganate oxidizes succinic acid to a mixture of malic and tartaric acid [133-37-9]. 3-Hydroxypropionic acid [503-66-2] is obtained with sodium perchlorate. Cerium(IV) sulfate in sulfuric acid medium oxidizes succinic acid to oxaloacetic acid (71). 

The moderate resistance of DMSO to oxidation permits it to be used as a solvent for oxidations with lead tetraacetate or the 2-nitropropane anion (33,34). Dichromate oxidation and permanganate oxidation have been used for quantitative deterrnination of DMSO (35,36). 

Many reactions catalyzed by the addition of simple metal ions involve chelation of the metal. The familiar autocatalysis of the oxidation of oxalate by permanganate results from the chelation of the oxalate and Mn (III) from the permanganate. Oxidation of ascorbic acid [50-81-7] C HgO, is catalyzed by copper (12). The stabilization of preparations containing ascorbic acid by the addition of a chelant appears to be negative catalysis of the oxidation but results from the sequestration of the copper. Many such inhibitions are the result of sequestration. Catalysis by chelation of metal ions with a reactant is usually accomphshed by polarization of the molecule, faciUtation of electron transfer by the metal, or orientation of reactants. 

There are many synthetic routes to alloxan. Probably the best is direct oxidation of barbituric acid (1004 R = H) with chromium trioxide (5208(32)6) but it may be made from barbituric acid via its benzylidene derivative by direct or indirect oxidation of uric acid from 5-chlorobarbituric acid (1004 R = C1) by nitration or from 5-nitrobarbituric acid (1004 R = N02) by chlorination, both via the intermediate (1005) (64M1057) or by permanganate oxidation of uracil (1006) under carefully controlled conditions (73BSF1167). 

The cleavage of fused pyrazines represents an important method of synthesis of substituted pyrazines, particularly pyrazinecarboxylic acids. Pyrazine-2,3-dicarboxylic acid is usually prepared by the permanganate oxidation of either quinoxalines or phenazines. The pyrazine ring resembles the pyridine ring in its stability rather than the other diazines, pyridazine and pyrimidine. Fused systems such as pteridines may easily be converted under either acidic or basic conditions into pyrazine derivatives (Scheme 75). 

Tropolone has been made from 1,2-cycloheptanedione by bromination and reduction, and by reaction with A -bromosuccinimide from cyolo-heptanone by bromination, hydrolysis, and reduction from diethyl pimelate by acyloin condensation and bromination from cyclo-heptatriene by permanganate oxidation from 3,5-dihydroxybenzoic acid by a multistep synthesis from 2,3-dimethoxybenzoic acid by a multistep synthesis from tropone by chlorination and hydrolysis, by amination with hydrazine and hydrolysis, or by photooxidation followed by reduction with thiourea from cyclopentadiene and tetra-fluoroethylene and from cyclopentadiene and dichloroketene. - ... 

Chloro-2,2,3-trifluoropropionic acid has been prepared by permanganate oxidation of 3-chloro-2,2,3-trifluoropropanol which is one of the telomerization products of chlorotrifluoroethylene with methanol. The present procedure is a modification of one reported earlier and is undoubtedly the method of choice for making propionic acids containing 2 fluorine atoms, i.e., 2,2,3,3-tetrafluoropropionic acid, 3,3-dichloro-2,2-difluoropropionic acid, and 3-bromo-2,2,3-trifluoropropionic acid. When preparing 2,2,3,3-tetrafluoropropionic acid from tetrafluoroethylene, it is desirable to use an additional 50 ml. of acetonitrile and externally applied heat to initiate the reaction. 

Stemonidine, CjoHajOgN. The base has m.p. 116 , [a]jf° — 7 65 , and yields a hydrochloride, m.p. 260 (dec.), and a methiodide, m.p. 248 . It is a tertiary base and of the five oxygen atoms two are in a lactone group and a third is present as methoxyl the functions of the other two are unknown. The alkaloid is unaffected by hydrogen chloride (25 per cent.) in alcohol or acetic acid. The permanganate oxidation products vary with the conditions of the experiment —... 

Potassium permanganate oxidation of a vinyl group to a carboxyl group can be used to prepare fluormated carboxyhc acids with aliphatic [3/ ] (equanon 30) or alicychc 39] (equation 31) skeletons... 

Similarly, permanganate oxidation of a number of naturally occurring canthin-6-one derivatives (295) leads to j8-carboline-l-carboxylic acid or its methyl ester.A j8-carboline-l-carboxylic acid... 

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