Arene thiolation

The photoinduced reactions of aryl halides with the thiourea anion afford arene thiolate ions in DMSO. These species can be used without isolation for... 

Analogous substitution reactions take place with alkane- and arene-thiolate anions <73JCS(P1)16S9), and pyridine-2- and -4-thiones are usually prepared by use of sodium or potassium hydrogen sulfide or thiourea (74JCS(P1)2300). 

An extensive range of complexes of the type [MoOTp XY] (X, Y = halide and/or alkoxide, aryloxide, alkyl or arene thiolate, bidentate 1,2-arenediolates, arenedithiolates, ethane diolates, and dithiolates) has been prepared. These octahedral species underwent quasi-reversible one-electron reductions... 

The reaction of trifluoromethyl iodide with arene thiolates provides trifluoromethyl aryl sulfides via a single electron transfer (SET) reaction rather than the SN2 reaction, which is the only formal mechanism (Scheme 2.31). In general, perfluoroalkyl (Rf—X), ferf-alkyl, and vinyl and aromatic halides are strongly deactivated for the replacement of halogens with... 

Special thiol carboxylic esters (29) were prepared fiom aroyl halides and arene thiolates. These 4,4 -disubstituted S-aiyl arenecarbothioates might gain importance hrtnn a practical point of view, since they exhibit liquid crystal properties and could be useful as components of a di lay cell. Another thiocarboxylic ester (30), which was obtained from a zinc thiochelate and benzoyl chloride (equation 19), might be potentiaUy useful as a precursor for organic conductors. 

Nucleophilic Substitution.— The reactivities of 2-halogeno-thiazoles with arenethiols are explained by the existence of an acid-base equilibrium preceding the substitution step the formation of an ion-pair or of thiazolium and arene-thiolate ions is the rate-determining step. Some 4- or 5-substituted 2-chloro-thiazoles apparently react with methoxide ion in a normal aza-activated nucleophilic substitution, the reaction being influenced by the substituent. In the case... 

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