Diphenyl sulfide, reaction with

Reactions with Sulfur Compounds. Thiosuccinic anhydride [3194-60-3] is obtained by reaction of diethyl or diphenyl succinate [621-14-7] with potassium hydrogen sulfide followed by acidification (eq. 10). Thiosuccinic anhydride is also obtained from succinic anhydride and hydrogen sulfide under pressure (121). 

This dialkoxydiphenylsulfurane has been prepared by the reaction of diphenyl sulfide, 2,2,2-trifluoro-l-phenyl-l-(trifluoromethyl)ethyl hypochlorite, and potassium l,l,l,3,3,3-hexafluoro-2-phenyl-2-propanolate and by the reaction of diphenyl sulfide with 1 equivalent of chlorine and 2 equivalents of potassium 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanolate in diethyl ether. ... 

Similar to nitrogen compounds, electron-rich sulfur compounds, such as the sulfides, with the lone pair of electrons on the sulfur atom, are oxidized to sulfoxides and, further, to sulfones by the H202/titanosilicate sytem (218,232, 233). Table XXXI (232) illustrates typical conversions and product selectivities for various sulfides for the reactions catalyzed by TS-1. Bulky sulfides such as alkyl, phenyl sulfides are relatively unreactive because of their steric exclusion from the pores of TS-1. Diphenyl sulfide could not be oxidized at all. As the diffusivity and, hence, the conversion of the sulfide decreases, the further oxidation of the primary product (sulfoxide) becomes more competitive, leading to increased formation of the corresponding sulfone (Table XXXI) ... 

The direct high yield synthesis of oxaspiropentanes from almost any type of aldehyde or ketone represents a particularly useful transformation because of the high reactivity of such compounds. This approach proves to be exceptionally simple. The DMSO reaction mixture can be directly extracted with pentane or hexane, the hydrocarbon solvent removed and the product isolated by distillation or crystallization. Since diphenyl sulfide is the only by-product extracted with the oxaspiropentane, the mixture can normally be used for most further synthetic transformations. Table 2 summarizes some of the oxaspiropentanes prepared by this method. 

The reaction of 15 with diphenyl ether and diphenyl sulfide yields poly(ether ketone) (11) and poly(sulfide ketone) (13) with exclusively para-substituted benzene rings according to Scheme 8. 

The salts (294) (Section VII, J, 1) are useful intermediates for the preparation of other meso-ionic systems by reaction with appropriate nucleophiles. Thus, reaction with sodium sulfide in dimethyl formamide yields the l,2,3,4-tetrazole-5-thiones (295), a new class of meso-ionic heterocycle. The 1,3-diphenyl derivative (295, R = = Ph) has a... 

The oxidation of sulfides to sulfoxides (1 eq. of oxidant) and sulfones (2 eq. of oxidant) is possible in the absence of a catalyst by employing the perhydrate prepared from hexafluoroacetone or 2-hydroperoxy-l,l,l-trifluoropropan-2-ol as reported by Ganeshpure and Adam (Scheme 99 f°. The reaction is highly chemoselective and sulfoxidation occurs in the presence of double bonds and amine functions, which were not oxidized. With one equivalent of the a-hydroxyhydroperoxide, diphenyl sulfide was selectively transformed to the sulfoxide in quantitative yield and with two equivalents of oxidant the corresponding sulfone was quantitatively obtained. 2-Hydroperoxy-l,l,l-fluoropropan-2-ol as an electrophilic oxidant oxidizes thianthrene-5-oxide almost exclusively to the corresponding cw-disulfoxide, although low conversions were observed (15%) (Scheme 99). Deprotonation of this oxidant with sodium carbonate in methanol leads to a peroxo anion, which is a nucleophilic oxidant and oxidizes thianthrene-5-oxide preferentially to the sulfone. 

The Baeyer-Villiger process for conversion of open-chain ketones to esters, or cyclic ketones to lactones by a peracid involves an intermediate a-hydroxyperester (235) step, as shown in equation 83. Determination of 235 in the reaction mixture involves selective reduction of the peroxyacid with diphenyl sulfide and reduction of 235 with excess iodide, followed by titration of the liberated iodine. The presence of various transition metal ions may affect the determination by accelerating the final step of the synthetic process, thus... 

The proposed mechanism of the oxidative cleavage of S-protecting groups by the chlorosilane/sulfoxide procedure is outlined in Scheme 8. 95 The first reaction is considered to be formation of the sulfonium cation 9 from diphenyl sulfoxide (7) and the oxygenophilic silyl compound 8. The formation of a sulfonium ion of this type is known and has been utilized for the reduction of sulfoxides. 97 Subsequent electrophilic attack of 9 on the sulfur atom of the S-protected cysteine residue leads to the formation of intermediate 10, whereby the nature of the silyl chloride employed should be the main factor that influences the electrophilicity of 9. The postulated intermediate 10 may then act as the electrophile and react with another S-protected cysteine residue to generate the disulfide 11 and the inert byproduct diphenyl sulfide (12). This final step is analogous to the reaction of a sulfenyl iodide as discussed in Section 6.1.1.2.1. 

Hydroxysulfenylation. Hydroxysulfenylation of cyclohexene is possible with diphenyl disulfide in CH2C12—TFA under air in the absence of a metal salt, but the reaction requires several days at 25°. With Pb(OAc)4 reaction occurs in 30 minutes at 0°. Actually Mn30(0Ac)7 is as efficient as Pb(OAc)4, particularly in reactions with dibenzyl disulfide. The trifluoroacetoxy sulfides can be converted into acetamido sulfides by reaction with acetonitrile containing cone. H2S04 (Ritter reaction, equation I).1... 

This however is not the whole story, for resinous products, oxalic acid, and ammonia are also formed. If the reaction with caustic alkali is carried out in the presence of thiophenol, some glycerin is formed and the thiophenol is oxidized to diphenyl sulfide. Alkali sulfides, K2S, KHS, and CaS, also yield glycerin. 

Under similar conditions, diphenyl sulfide, C6H5-S-C6H5, was found to be unreactive, indicating that the reactions listed in Table XII take place inside the pore structure, which is not accessible to bulky molecules such as diphenyl sulfide. The selectivity to sulfoxides (Table XII) is the result of a competition between sulfides and sulfoxides for the catalytic site dimethyl sulfide competes effectively, and the selectivity to sulfoxide is 97% with only 3% sulfone produced. The other reactant molecules give larger amounts of sulfones. However the reaction of dimethyl sulfide was carried out at 298 K, whereas the other sulfides reacted at the reflux temperature of acetone the temperature difference may explain part of the differences shown in Table XII. 

Reactions of phosphines and phosphites have received some attention but their preparative value is limited. The zwitterion formed from diphenylmethylphosphine and benzyne rearranges to ylide (124) which can be captured by Wittig alkenation, with cyclohexanone, in about 20% yield.159 Some synthetically useful reactions of tellurium and selenium compounds with arynes have been reported. For example, heating diphenyl iodonium carboxylate and bis(p-ethoxyphenyl) ditelluride in dichlorobenzene affords the compound (125).160 The corresponding reactions with diphenyl selenide and diphenyl sulfide... 

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