Manganese compounds sulfoxides

The most important applications of peroxyacetic acid are the epoxi-dation [250, 251, 252, 254, 257, 258] and anti hydroxylation of double bonds [241, 252, the Dakin reaction of aldehydes [259, the Baeyer-Villiger reaction of ketones [148, 254, 258, 260, 261, 262] the oxidation of primary amines to nitroso [iJi] or nitrocompounds [253], of tertiary amines to amine oxides [i58, 263], of sulfides to sulfoxides and sulfones [264, 265], and of iodo compounds to iodoso or iodoxy compounds [266, 267] the degradation of alkynes [268] and diketones [269, 270, 271] to carboxylic acids and the oxidative opening of aromatic rings to aromatic dicarboxylic acids [256, 272, 271, 272,273, 274]. Occasionally, peroxyacetic acid is used for the dehydrogenation [275] and oxidation of aromatic compounds to quinones [249], of alcohols to ketones [276], of aldehyde acetals to carboxylic acids [277], and of lactams to imides [225,255]. The last two reactions are carried out in the presence of manganese salts. The oxidation of alcohols to ketones is catalyzed by chromium trioxide, and the role of peroxyacetic acid is to reoxidize the trivalent chromium [276]. 

In addition, manganese oxide oxidizes benzylic methyl or methylene to carbonyl [814] and cleaves the carbon bonds of vicinal diols [577, 522]. It converts amines into imines [577, 525] tertiary amines into secondary amines [572], formamides [526, 527, 525], or ketones aromatic primary amines [575, 525] and hydrazo compounds [525] into azo compounds hy-droxylamines into nitroso [576] or nitro compounds [525] hydrazones into diazo compounds [520] phosphines into phosphine oxides [575] thiols into disulfides [576] and sulfides into sulfoxides [541]. 

Porphyrin compounds can often act as efficient catalysts in the oxidation of hydrocarbons, carbonyl compounds and sulfides and their efficiency is frequently improved when they are supported on an inorganic solid. For example, in the presence of an iron or manganese porphyrin iodo-sylbenzene oxidises sulfides to give sulfoxides but over-oxidation often occurs, yielding sulfones. When the porphyrin is supported on silica the over-oxidation is suppressed and the yield of sulfoxide is raised. In this process it is believed that the sulfoxides are adsorbed onto the solid immediately after they are generated and so undergo no further reaction... 

Oxidations. WChlorosuccinimide-dimethyl sulfide (NCS-DMS) is one of several reagents for converting alcohols to alkoxydtmethylsulfonium salts, which in the presence of base convert to the corresponding carbonyl compounds via intramolecular proton transfer and loss of dimethyl sulfoxide. These oxidations are among the mildest and most selective for conversions of alcohols to aldehydes and ketones. This reaction does not suffer the overoxidation to acids or the carbon-carbon bond cleavages which are often encountered in chromium(VI) or manganese(VII) oxidations (eq 1). ... 

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