Cuprous phenylmercaptide

The present procedure has also been used by the submitters to prepare the following thioethers l,4-bis-( -butylthio)benzene, pale yellow oil, b.p. 142°/0.S mm., Mq 1.5726, from -dibromo-benzene and cuprous -butylmercaptide (yield 68-74%) 1,2-bis(phenylthio)benzene, white ciystals, m.p. 42.5-44.5°, b.p. 190°/1 mm., from o-dibromobenzene and cuprous phenylmer-captide (see below) (yield 79-83%), or from i>-dichlorobenzene (see below) and cuprous phenylmercaptide (yield 58-71%) l,4-bis(phenylthio)benzene, white crystals, m.p. 82-83°, from / -dibromobenzene and cuprous phenylmercaptide (yield 80-84%), or from -dichlorobenzene (see below) and cuprous phenylmercaptide (yield 59-72%). The same method can be applied to the preparation of many other thioethers. 

Cuprous phenylmercaptide is prepared from cuprous oxide and benzenethiol according to the procedure given for cuprous -butylmercaptide. A heating period of only 2 hours (when freshly prepared cuprous oxide is used), however, is required to obt the yellow compound. Chloro compounds can be used instead of bromo compounds for the reaction with cuprous phenylmercaptide. However, a higher reaction temperature (210-220°) and a longer reaction time (24 hours) is required. 

The necessary pot temperature is obtained by using a mixture of 350 ml. of quinoline and 8 ml. of pyridine as solvents. It is also advantageous to use a larger excess of cuprous phenylmercaptide (121 g., 0.69 mole). 

B is( -butylthio)benzene and 1,4-bis( -butylthio)benzene have been prepared from the corresponding dibromobenzene and cuprous w-butylmercaptide, using a mixture of quinoline and pyridine as solvent.6, l,2-Bis(phenylthio)benzene and 1,4-bis(phenylthio)benzenehave been prepared from the corresponding dichloro- or dibromobenzenes and cuprous phenylmercaptide, using a mixture of quinoline and pyridine as solvent.5 1,4-Bis(phenylthio)benzene has also been prepared from -dibromo-benzene or -bromophenyl phenyl sulfide and lead phenylmercaptide 7 and from diazotized 4-aminophenyl phenyl sulfide and sodium phenylmercaptide.8... 

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