Disulfides aromatic, oxidation

Under aprotic conditions, prototropic transformations of thiols are relatively slow, so one can observe distinct waves of the oxidation of the protonated form and of its parent base [19, 20]. Normally, the oxidation of thiols (aliphatic, aromatic, and heteroaromatic) affords diorganyl-disulfides. So various aliphatic and aromatic thiols are easily converted into the corresponding disulfides upon oxidation in MeOH/MeONa with the yields ranging... 

It is a colorless liquid boils at 206°.5 (403°.7 F.) has an aromatic odor is insoluble in water, soluble in all proportions in alcohol, ether, and carbon disulfid. By oxidation it yields, first, benzoic aldehyde, C Hi(COH) and afterward, benzoic acid, CaHeiCOOH). By the same means it may be made to yield products similar to those obtained from the alcohols of the saturated hydrocarbons. 

Organic sulfur compounds such as sulfurized spermaceti oil, terpene sulfides, and aromatic disulfides have been used. Encumbered phenols such as di-tertiary-butylphenols and amines of the phenyl-alphanaphthylamine type are effective stopping the kinetic oxidation chain by creating stable radicals. 

The reactive species that iaitiate free-radical oxidatioa are preseat ia trace amouats. Exteasive studies (11) of the autoxidatioa mechanism have clearly estabUshed that the most reactive materials are thiols and disulfides, heterocycHc nitrogen compounds, diolefins, furans, and certain aromatic-olefin compounds. Because free-radical formation is accelerated by metal ions of copper, cobalt, and even iron (12), the presence of metals further compHcates the control of oxidation. It is difficult to avoid some metals, particularly iron, ia fuel systems. 

In an attempt to protect thiophenols during electrophilic substitution reactions on the aromatic ring, the three substituted thioethers were prepared. After acetylation of the aromatic ring (with moderate yields), the protective group was converted to the disulfide in moderate yields, 50-60%, by oxidation with hydrogen peroxide/boiling mineral acid, nitric acid, or acidic potassium permanganate. ... 

Polythiosemicarbazide disulfide is the most efficient aliphatic polyamine disulfide for inhibiting the thermal oxidative breakdown of polypropylene, while polyimi-noaniline disulfide and polydiiminodiphenyloxide disulfide (Fig. 3) are the most efficient aromatic polyamine disulfides. In contrast to polyethylene, the thermal oxidative breakdown period increases as the concentration increases (Fig. 4), Depending on the concentration, the flow-melt index at 230°C increases at a lower rate than in the case of commercial stabilizer Santanox (Table 2)-... 

Sulfinic esters, aromatic, by oxidation of disulfides in alcohols, 46, 64 Sulfonation ot d,l camphor to d,l-10-camphorsulfomc acid, 45,12 Sulfoxides, table of examples of preparation from sulfides with sodium metapenodate, 46,79 Sulfur dioxide, reaction with styrene phosphorus pentachlonde to give styrylphosphomc diclilonde, 46,... 

Optically active aromatic thiosulfinates were first prepared by asymmetric oxidation of diaryl disulfides with (+)-percamphoric acid (105,112). Apart from the fact that the optical purity of diaryl... 

The oxidation of a mixture of aromatic disulfides, Ph2S2 or T0I2S2, with 2,2,2,-trifluoroethylamine affording arylsulfany-lation of the amino group was reported (Eq. 23) [138]. 

In the photochemical one-electron oxidation of aromatic sulfides, dimer radical cations were formed in rapid equilibrium with monomeric radical cation (59). The complex formation of a- and tt-types has been shown to be sensitive to the steric and electronic influence of substituent. For the case of jo-(methylthio)anisole the formation of TT-type dimer was shown to be reduced due to steric hindrance of two methyl groups. No formation of dimer radical cation was observed for jo-(methoxy)thioanisole and diphenyl disulfide where the corresponding monomer radical cations are stabilized by the delocalization of positive charge on the sulfur atom. Density-functional calculations supported the experimental results. The intramolecular formation of similar radical... 

Similar behavior of other aromatic disulfides and thiols on gold electrodes has been described based on the SERS experiments [167]. Adsorption of benzenethiol, benzenemethanethiol, p-cyanobenzenemethanethiol, diphenyl sulfide, and dibenzyl sulfide was studied on the roughened gold electrode. All these species adsorb dissociatively as the corresponding thiolates. Monolayers formed from symmetric disulfides were exactly like those formed from the corresponding thiols. These monolayers were stable in a wide potential window from -1-800 to —1000 mV (versus SCE), which was limited by the oxidation of the Au surface from the positive side and hydrogen evolution at —1000 to —1200 mV at the negative side. 

Aralkyl disulfides, 58, 142 Arenediazonium fluoborates, 58, 137 ARENE OXIDES, 58, 12, 15 Aristolone, 58, 162, 163 Aromatic compounds, carboxylation of, 56, 28... 

In addition to the sulfur compounds listed above, hydrogen sulfide has been found in many crude petroleums. Elemental sulfur has been definitely found in several crude petroleums by API Research Project 48 (23). Although Birch and Norris (5) isolated several disulfides from the spent caustic used in treating gasoline from Iranian petroleum, these compounds may have resulted from the oxidation of the thiols and their presence in the original petroleum is regarded as doubtful. Other types of sulfur compounds, such as thiophenes and aromatic thiols, have been identified in cracked petroleum products, but the presence of such compounds in naturally occurring petroleums has not yet been established. 

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