Disulfides, RSSR

Oxidation. Disulfides are prepared commercially by two types of reactions. The first is an oxidation reaction uti1i2ing the thiol and a suitable oxidant as in equation 18 for 2,2,5,5-tetramethyl-3,4-dithiahexane. The most common oxidants are chlorine, oxygen (29), elemental sulfur, or hydrogen peroxide. Carbon tetrachloride (30) has also been used. This type of reaction is extremely exothermic. Some thiols, notably tertiary thiols and long-chain thiols, are resistant to oxidation, primarily because of steric hindrance or poor solubiUty of the oxidant in the thiol. This type of process is used in the preparation of symmetric disulfides, RSSR. The second type of reaction is the reaction of a sulfenyl haUde with a thiol (eq. 19). This process is used to prepare unsymmetric disulfides, RSSR such as 4,4-dimethyl-2,3-dithiahexane. Other methods may be found in the Hterature (28). 

Thiocyanogen [(SCN)2, 5°, 4 h, 40% yjeld] selectively oxidizes an 5-tri-phenylmethyl thioether to the disulfide (RSSR) in the presence of an 5-di-phenylmethyl thioether. ... 

However, a strong caustic solution is used to remove mercaptans from gas and liquid streams. In the Merox Process, for example, a caustic solvent containing a catalyst such as cobalt, which is capable of converting mercaptans (RSH) to caustic insoluble disulfides (RSSR), is used for streams rich in mercaptans after removal of H2S. Air is used to oxidize the mercaptans to disulfides. The caustic solution is then recycled for regeneration. The Merox process (Fig. 1-3) is mainly used for treatment of refinery gas streams. ... 

Thiols can be oxidized by Br2 or I2 to yield disulfides (RSSR )- The reaction is easily reversed, and a disulfide can be reduced back to a thiol by treatment with zinc and acid. 

A hydroxy and an arylthio group can be added to a double bond by treatment with an aryl disulfide and lead tetraacetate in the presence of trifluoroacetic acid." Manganese and copper acetates have been used instead of Pb(OAc)4. ° Addition of the groups OH and RSO has been achieved by treatment of alkenes with O2 and a thiol (RSH)." Two RS groups were added, to give vie- dithiols, by treatment of the alkene with a disulfide RSSR and Bp3-etherate."° This reaction has been carried... 

TiCU, SiCl4, with a disulfide (RSSR R = alkyl or aryl), ° or with methylthio-trimethylsilane (MeSSiMe3). ... 

Unsymmetrical disulfides can be prepared by treatment of a thiol RSH with diethyl azodicarboxylate (EtOOCN=NCOOEt) to give an adduct, to which another thiol R SH is then added, producing the disulfide RSSR. ... 

Peroxides are cleaved to 2 mol of alcohols by L1A1H4 or by catalytic hydrogenation. Peroxides can be reduced to ethers with P(OEt)3. ° In a similar reaction, disulfides (RSSR ) can be converted to sulfides (RSR ) by treatment with tris(diethylamino)phosphine, (Et2N)3P. ... 

Devise a competition method which allows the determination of the rate of reaction of P—SH with another disulfide RSSR which does not lead to a colored species... 

There are three possible types of three-electron bonds. Oxidation of a u bond leads to a cation-radical with a, u three-electron bond. This bond contains no antibonding electrons, and the total bond strength exceeds that of a double bond by the energy of half a n bond. Olefins can acquire the 2a—In bond on one-electron oxidation, the bond constructed from the electrons 2a and In. Oxidation of organic disulfides, RSSR, to their cation-radicals (RSSR) yields species in which the unpaired electron from the oxidized sulfur interacts with the unbound p-electron pair of the second sulfur (Glass 1999). This establishes a 2n-In bond on top of the already existing o bond. The overall bond strength of this five-electron (2a—2n-In ) bond also exceeds that of the normal... 

There is also an expectation that thiols can be directly oxidized through to disulfides (RSSR in Fig. 4.4B) (Mestres et ah, 2000 Rauhut et ah, 1996), a mechanism also suggested for the case of 3MH (Murat et ah, 2003) where a protective effect from anthocyanins present in the wine was noted. In one study, the concentrations of both ethanethiol and the related oxidized form of diethyl disulfide in a red wine were found to decrease over a 60-day period, and at a greater rate under aeration (Majcenovic et ah, 2002). However, in a survey of wines over five vintages, the older wines were shovm to contain higher concentrations of diethyl disulfide, and lower concentrations of ethanethiol (Fedrizzi et ah, 2007). 

Thiols can be prepared by the reduction of sulfonyl halides652 with LiAIH4. Usually, the reaction is carried out on aromatic sulfonyl chlorides. Zinc and acetic acid, and HI. also give the reduction. Sulfonic acids have been reduced to thiols with a mixture of triphenyl-phosphine and either Ii or a diaryl disulfide.633 Disulfides RSSR can also be produced.634 For the reduction of sulfonyl chlorides to sulfinic acids, see 0-118. 

Disulfides, RSSR, and methylsulfanyl chloride are converted29 into the sulfur(IV) and sulfur(VI) compounds RSF3 (56-61 % with R = Ph) and RSF5 by treatment with silver(II) fluoride in the liquid phase. RSeF3 compounds are prepared similarly.119... 

Some literature supporting this point of view should be mentioned. An exchange reaction of the two diorganyl disulfide moieties results in the formation of the assymetric disulfide RSSR (R and R are different alkyls) ... 

Aromatic and aliphatic thioles RSH (R = 2-, 3-, or 4-tolyl, 2-hydroxyethyl, 2-ethoxyethyl, 4-chlorphenyl, etc.) in the presence of a base yield anionic dithiolatorhodium(III) porphyrins (path j) which show the so-called hyperporphyrin spectra and are susceptible to autoxidation yielding hyperoxide ions. Although the formation of the latter ones is formulated via a nucleophilic exchange of coordinated OJ with thiolate, it could well be that an outer-sphere electron transfer between he anionic bis(thiolato) complex and molecular dioxygen initiates the observed formation of disulfides RSSR. 

The types of organosulfur compounds found in petroleum feedstocks are shown in Table Of them, the alkyl and aryl thiols (RSH), sulfides (RSR ), and disulfides (RSSR ) are the most rapidly desulfurized (equation 1). It is the broad class of thiophenes, stabilized by their aromatic character, that are most difficult to desulfurize and require relatively severe temperatures ( 400 °C) and H2 pressures ( 100 atm). Thus, it is the HDS of thiophenes that has been of greatest interest to inorganic and organometallic chemists. There are fewer model studies of the HDS of thiols, sulfides, and disulfides. Organometallic aspects of HDS and HDN have been summarized most comprehensively in a recent book by Sanchez-Delgado. A briefer overview has also been published. More specific reviews are cited in later sections of this chapter. 

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