Diphenyl sulphide

Crystallisable polymers have also been prepared from diphenylol compounds containing sulphur or oxygen atoms or both between the aromatic rings. Of these the polycarbonates from di-(4-hydroxyphenyl)ether and from di-(4-hydroxy-phenyl)sulphide crystallise sufficiently to form opaque products. Both materials are insoluble in the usual solvents. The diphenyl sulphide polymer also has excellent resistance to hydrolysing agents and very low water absorption. Schnell" quotes a water absorption of only 0.09% for a sample at 90% relative humidity and 250°C. Both the sulphide and ether polymers have melting ranges of about 220-240°C. The di-(4-hydroxyphenyl)sulphoxide and the di-(4-hydroxy-phenyl)sulphone yield hydrolysable polymers but whereas the polymer from the former is soluble in common solvents the latter is insoluble. 

Olah and coworkers56 found that treatment of dialkyl, arylalkyl and diaryl sulphides with nitronium hexafluorophosphate (or tetrafluoroborate) 32 at —78° in methylene chloride resulted in the formation of sulphoxides in moderate to high yields (Table 3). In the oxidation of diphenyl sulphide which affords diphenyl sulphoxide in 95% yield, small amounts of the ring nitration products (o- and p-nitrophenyl phenyl sulphides) were formed. However, diphenyl sulphone and nitrophenyl phenyl sulphoxide were not detected among the reaction products. 

Diphenyl sulphoxide was obtained when a solution of diphenyl sulphide was treated with potassium hydrogen sulphate in ethanol and acetic acid131. 

If a mixture of diphenyl sulphide and the corresponding sulphoxide are treated with osmium tetroxide in boiling ether for 48 hours the sulphide is unchanged whilst the sulphoxide is converted into the sulphone in 96% yield with concomitant production of osmium trioxide140. It thus seems that this method would be useful synthetically for the preparation of sulphones from sulphoxides containing sulphide functionalities. Ruthenium tetroxide may be used in place of osmium(VIII) oxide148. 

Although this mechanism could explain the inertness of di-t-butyl sulphide towards oxidation due to the absence of a-hydrogen atoms, it was later ruled out by Tezuka and coworkers They found that diphenyl sulphoxide was also formed when diphenyl sulphide was photolyzed in the presence of oxygen in methylene chloride or in benzene as a solvent. This implies that a-hydrogen is not necessary for the formation of the sulphoxide. It was proposed that a possible reactive intermediate arising from the excited complex 64 would be either a singlet oxygen, a pair of superoxide anion radical and the cation radical of sulphide 68 or zwitterionic and/or biradical species such as 69 or 70 (equation 35). 

Examples of such reactions are well known. Sloan, Breslow, and Renfrow found that both alkane and arenesulphonyl azides insert into the carbon-hydrogen bonds of saturated hydrocarbons 12>. Thus, 1-pentane,- 2-propane- and -toluene-sulphonyl nitrene inserted into cyclohexane to give 54, 60, and 58% yields of the corresponding IV-cyclohexylamide derivatives 8>. Similarly, 2-phenoxybenzene-, diphenyl sulphide-2-, and... 

Diphenyl sulphide []39-66-2] M 186.3, b 145 /8mm, d 1.114, n 1.633. Washed with aqueous 5% NaOH, then water. Dried with CaCl2, then with sodium. The sodium was filtered off and the diphenyl sulphide was distd under reduced pressure. 

The latter compound on oxidation again yields the sulphonic acid. Again, sulphuryl chloride reacts with benzene in the presence of aluminium chloride to give diphenylsulphone, (C6H5)2S02, a compound which can also be obtained by oxidation of diphenyl sulphide, (C6H5)2S. On the assumption that the phenyl radicals remain attached to the sulphur atom throughout these transformations, it is obvious that the hydroxyl radicals in sulphuric acid must also be directly attached to sulphur. 

Diphenyl selenide is a colourless, strongly refractive oil, B.pt. 167° C. at 16-5 mm. insoluble in water but miscible with alcohol or ether in all proportions. It has a faint odour, and a density of 1 3712 at 0° C., 1 3561 at 15 2° C., and 1 350 at 20° C. With cold bromine in ether solution it yields the dibromide. Diphenyl selenide, unlike dimethyl selenide, does not combine with alkyl iodides, and in this respect it resembles diphenyl sulphide.2 When heated nearly to its boiling-point with sulphur it gives diphenyl sulphide, the reaction being practically quantitative at 300° C.3 With palladium chloride it forms the complex PdCl2.2(C6H5)2Se, orange-red needles, M.pt. 181° to 182° C.4... 

Diederich et al. had postulated that the highly reactive iron-oxo species, arising from oxygen transfer from the oxidant to the Fem site [87], should be greatly stabilised by enclosure within a dendritic superstructure. The catalytic potential of the dendrimers 6 a-c was determined in the epoxidation of alkenes [83 a, 88] (1-octene and cyclooctene) and the oxidation of sulphides [83 a] ((methylsulphanyl)benzene and diphenyl sulphide) to sulphoxides - in dichloro-methane with iodosylbenzene as oxidising agent. Compared to the known metal-porphyrin catalysts, 6a-c exhibit only low TON (7 and 28, respectively, for... 

This highly reactive compound may be utilized for various reactions (Zincke [20, 21]). For example, with hydrogen sulphide it forms a tetranitro derivative of diphenyl sulphide (Zincke and Weisspfennig [22]). 

Sulphur, or sulphur-containing heterocyclics induce the formation of cokes of small sized optical texture (22) Mochida et al. (75) examined the carbonization behaviour, in the presence of aluminium chlorides, of diphenyl sulphide, thioxanthene and thianthrene,... 

Gragerov and Levit studied the oxidation of diphenyl sulphide by peroxomonosulphate in ethanol-acetic acid solvent containing H2 0, and found that the products, diphenyl sulphoxide and diphenyl sulphone, were unlabelled. They concluded that the oxidation is heterolytic and does not involve free-radicals. 

When heated at 150° C. phenylmercuric acetate gives carbon, benzene, mercury, oxygen, and acetic anhydride. Dry distillation yields mercury, diphenyl oxide, and acetic anhydride. Distillation with sulphur gives mercury, benzene, acetic acid, acetic anhydride, and diphenyl sulphide. Boiling with dilute sulphuric or hydrochloric acid produces benzene, acetic acid, and a mercuric salt. The acetate is reduced by nascent hydrogen to benzene, mercury, and acetic acid. 

Lead diphenyl sulphide.—When an aqueous acetic acid solution of the above acetate is decomposed with hydrogen sulphide, a white, fiocculent precipitate of the sulphide is obtained. By extracting this with alcohol-benzene, and evaporating off the solvent, small, bright yellow crystals are deposited. It is essential that the reaction should be carried out in the cold, since the sulphide is decomposed by heat. The compound becomes brown when heated from 80° to 90° C., and at higher tehaperatures diphenyl is driven off, and pure lead sulphide remains. The salt is easily soluble in benzene, chloroform, or carbon bisulphide, but with difficulty in alcohol or ether. 

A number of triphenylbismuthonium diacylylides and also the diphenylsulphonylylide undergo transylidation when treated with dimethyl sulphide in the presence of copper(I) chloride in benzene at room temperature, giving the corresponding dimethylsulphonium ylides no such reaction took place with diphenyl sulphide Some of these bismuthonium ylides reacted with triphenylarsine or triphenylphosphine and were converted thereby into arsonium or phosphonium ylides they did not react with triphenylstibine L The conversion of the diacetylylide into the 4,4-dimethyl-2,6-dioxocyclohexylide as mentioned in Section IX.A should also be noted. 

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