Organic oxides thiols

Several organic compounds may oxidize thiols to disulphides or to products of further oxidation in a variety of experimental conditions. We shall briefly deal in this section with some of the more characteristic cases. 

Because thiols are easily oxidized, a host of organic and inorganic oxidants may be used. Mild oxidants such as oximes, nitro compounds, or air can be effective. Various oxidants have been used in special appHcations, but only a few are used in large-scale appHcations. 

The principal mbbers, eg, natural, SBR, or polybutadiene, being unsaturated hydrocarbons, are subjected to sulfur vulcanization, and this process requires certain ingredients in the mbber compound, besides the sulfur, eg, accelerator, zinc oxide, and stearic acid. Accelerators are catalysts that accelerate the cross-linking reaction so that reaction time drops from many hours to perhaps 20—30 min at about 130°C. There are a large number of such accelerators, mainly organic compounds, but the most popular are of the thiol or disulfide type. Zinc oxide is required to activate the accelerator by forming zinc salts. Stearic acid, or another fatty acid, helps to solubilize the zinc compounds. 

The various oxidation states of sulfur have been determined by polarography. The electrochemical oxidation of sulfide ions in aqueous solution may lead to the production of elementary sulfur, polysulfides, sulfate, dithionate, and thiosulfate, depending on the experimental conditions. Disulfides, sulfoxides, and sulfones are typical polarographically active organic compounds. It is also found that thiols (mer-captans), thioureas, and thiobarbiturates facilitate oxidation of Hg resulting thus in anodic waves. 

Organic peroxides such as cumene hydroperoxide and t-butyl hydroperoxide have extensively been used as experimental agents. They provoke lipid peroxidation in hepatocytes, probably by the generation of alkoxyl and peroxyl radical intermediates after reaction with cytochrome P450. Other cytotoxic mechanisms are probably involved including protein thiol and non-protein thiol oxidation and deranged calcium homeostasis (Jewell et al., 1986). In fact, the addition of cumene hydroperoxide to isolated bUe duct cells, devoid of cytochrome P450 activity, still results in cell death but lipid peroxidation is not detectable (Parola et al., 1990). 

Contact of the sohd oxidant with organic thiols or sulfides may cause a violent reaction and flash fire [1]. This procedure was recommended formerly for treating spills of sulfur compounds [2,3], but is now withdrawn as potentially hazardous. Use of an aqueous solution of up to 15% concentration, or of 5% sodium hypochlorite solution is recommended [1]. Addition of 10 g of oxidant to 5 ml portions of... 

Barrett and coworkers have explored hetero-substituted nitroalkenes in organic synthesis. The Michael addition of nucleophiles to 1-alkoxynitroalkenes or 1-phenylthionitroalkenes followed by oxidative Nef reaction (Section 6.1) using ozone gives a-substituted esters or thiol esters, respectively.41 As an alternative to nucleophilic addition to l-(phenylthio)-nitroalkenes, Jackson and coworkers have used the reaction of nucleophiles with the corresponding epoxides (Scheme 4.4).42 Because the requisite nitroalkenes are readily prepared by the Henry reaction (Chapter 3) of aldehydes with phenylthionitromethane, this process provides a convenient tool for the conversion of aldehydes into ot-substituted esters or thiol esters. 

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