Phenyl sulphur chloride

The aromatic mercaptans react with chlorine to form aryl sulphur chlorides (Zincke) phenyl sulphur chloride is a deep red, very reactive liquid (Lecher) ... 

Diphenyl diselenide, (CeH5)2Se2, is formed as a by-product in the preparation of phenyl selenide when magnesium phenyl bromide in ether solution reacts with selenium.5 A 2 per cent, yield is obtained when benzene, aluminium and selenium bromides react in dilute carbon disulphide solution. The product melts at 62° C.6 The corresponding oxide is an oil, B.pt. 230° C. at 65 mm.,7 and the sulphide, (C6H5)2Se2S, M.pt. 55° C., is obtained from sulphur chloride and phenyl selenide in carbon disulphide solution.8... 

This compound will be referred to again in connection with the synthesis of salicylic acid (p. 717). The acid ester of phenol and sulphuric acid, phenyl sulphuric acid, CeHs—O—SO2OH, is a constituent of animal urine. The esters of phenols and organic acids are not readily formed by the direct action of the acids, in which respect the phenols again resemble tertiary alcohols. They may be prepared from phenols by the action of acid chlorides acid anhydrides or a mixture of the acid and phosphorus oxychloride. 

Benzyl phenyl sulphide, norbornene, cw-cyclooctene, and 4-vinyl-1-cyclohexene were obtained from Aldrich and (IS)-(-)-a-pinene from Fluka. Phenyl sulphide was prepared from benzene and sulphur chloride following the literature procedure[9]. Reference samples of sulphoxides and sulphones were prepared by oxidation of sulphides with sodium periodate[10] and hydrogen peroxide[ll] respectively. Reference samples of epoxides were made by following Kaneda et al.[ 2 procedure. Metal phthalocyanines[13] were prepared from appropriate metal salt, 1,2-dicyanobenzene with ammonium molybdate as catalyst and were characterized by elemental analysis. 

Place the distillate in a separating-funnel and extract the benzonitrile twice, using about 30 ml. of ether for each extraction. Return the united ethereal extracts to the funnel and shake with 10% sodium hydroxide solution to eliminate traces of phenol formed by decomposition of the benzenediazonium chloride. Then run off the lower aqueous layer, and shake the ethereal solution with about an equal volume of dilute sulphuric acid to remove traces of foul-smelling phenyl isocyanide (CaHjNC) which are always present. Finally separate the sulphuric acid as completely as possible, and shake the ether with water to ensure absence of acid. Run off the water and dry the benzonitrile solution over granular calcium chloride for about 20 minutes. 

After all the diethyl sulphate has been introduced, reflux the mixture gently for 2 hours with stirring. Transfer the diluted reaction mixture to a separatory funnel, run oflF the lower aqueous layer, wash successively with water, dilute sulphuric acid (twice), and with water until the washings are neutral to litmus. Dry over anhydrous calcium chloride or magnesium sulphate, and distil. Collect the phenyl ethyl ether (a colourless liquid) at 168-170°. The yield is 50 g. 

The phenyl propionate may be prepared by slowly adding 196 g. (120 ml.) of redistilled thionyl chloride to a mixture of I50g. of pure phenol and 132 g. (133 ml.) of propionic acid (compare Fig. 111,31, 1), warming to drive all the sulphur dioxide and hydrogen chloride, and distilling 190 g. of phenyl propionate, b.p. 202-212° (the pure substance boils at 211°) are obtained. 

This acid, CgHj. CH COOH, is a sweet-smelling substance, especially recommended for sweetening soap perfumes. It occurs in neroli oil, and has a sweet honey-like odour. It is formed by converting toluene into benzyl chloride which is converted into benzyl cyanide, which is digested with dilute sulphuric acid, and so converted into phenyl-acetic acid. It is a crystalline body, melting at 76° to 76 5° and Iwiling at 266°. It has been isolated from oil of neroli. 

Peroxybenzoic acid readily oxidizes aryl and alkyl sulphoxides in acetone, methylene chloride or chloroform solutions, to the sulphone in high yield . The reaction is second order and acid catalysed as is the reaction with peracetic acid . The rate of oxidation is about five times faster than when peracetic acid is used. Other work considering the oxidation of sulphoxides with peracids gathered kinetic evidence and showed that the reaction was indeed second order and that the reaction involved nucleophilic attack by the sulphoxide sulphur atom on the peracid moiety. A further study by the same authors showed that with benzyl and phenyl alkyl sulphoxides the rate of reaction was very sensitive to the inductive effect of the alkyl group. Support for the nucleophilic attack by the sulphur atom on the peracid in acidic solution was forthcoming from other sources . ... 

A. The Basic Series.—In general, aromatic aldehydes condense with aromatic amines in the presence of zinc chloride to form triphenylmethane derivatives (0. Fischer) phenols and phenyl ethers behave similarly in the presence of concentrated sulphuric acid (Baeyer). The products formed are the leuco-compounds of well-known dyes. 

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. 

Chlorinolysis is another reaction mode observed in some sulphides, in which sulphur retains its oxidation state. For example, phenyl trityl sulphide and benzyl trityl sulphide were converted into trityl chloride and sulphenyl chlorides [26]. Thiirane and thietane reacted similarly with 3-(dichloroiodo)pyridine to afford chlorinated disulphides [25] ... 

The mixture is stirred continuously and maintained for 3 hours at 15° C., when sodium phenyl arsenate is formed. This is neutralised with hydrochloric acid and filtered through a press in order to separate resinous substances which are formed. The phenyl arsenic acid in the filtrate is reduced to phenyl arsenious oxide by passing a current of sulphur dioxide through. A heavy oil deposits at the bottom of the vessel and this is removed by decantation and redissolved in 40° B. sodium hydroxide solution. After diluting with 8 cu. m. of water, the solution is cooled to 15° C. and run slowly into another solution of diazobenzene chloride prepared as before. The sodium salt of diphenyl arsenic acid which is formed is slightly acidified with hydrochloric acid, the diphenyl arsenic acid filtered off and redissolved in 20° B6. hydrochloric acid (i part of the arsenic acid requires 3 parts of hydrochloric acid) and the solution obtained is then run into an iron vessel, lined internally with tiles. Sulphur dioxide is then passed through for 8 hours while the temperature is maintained at about 80° C. Diphenyl chloroarsine then separates as an oil which forms a layer at the bottom of the vessel. It is separated off and dried in vacuo. 

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