Arenesulfenyl Chlorides Research Articles

Synthesis and Decomposition of Alkane- and Arenesulfonyl Aryl Disulfides

Abstract Pyridinium alkane- and arenethiolsulfonates were allowed to react with arenesulfenyl chlorides, CISAr′, to yield sulfonyl disulfides in which R is n-dodecyl, benzyl, phenyl, or p-tolyl group, and Ar′ o-nitrophenyl or o-nitro-p-chlorophenyl. p-Toluenesulfonyl p-nitrophenyl disulfide was also prepared by this method. IR and UV spectra of these compounds were determined and compared with those of the corresponding thiolsulfonates. Decomposition of 35S-labeled p-toluenesulfonyl p-nitrophenyl disulfide, p-CH3C6H4SO2S35SC6H4NO2-p, gave 35S-labeled p-nitrophenyl p-toluenethiolsulfonate, p-CH3C6H4SO235SC6H4NO2-p. Triphenylphosphine was found to attack two oxygen atoms and a sulfur atom of p-toluenesulfonyl o-nitrophenyl disulfide at the same rate. The reaction of triphenylphosphine with 35S-labeled p-toluenesulfonyl o- and p-nitrophenyl disulfides revealed that the central sulfur atom of these sulfonyl disulfides was desulfurated. This result coincides with that of the decomposition mentioned above. The susceptibility of sulfonyl disulfides containing p-nitrophenyl group to the decomposition and the desulfuration of the central sulfur atom of sulfonyl disulfides in general are also discussed.

The Reaction of Sulfenyl Chlorides with Thioethers. III. The Configuration and the Isomerization of cis- and trans-α-Methylthio-β-phenylthiostyrenes

Abstract Various α-methylthio-β-arylthiostyrenes were prepared by the action of arenesulfenyl chloride on α-methylthiostyrene. The configuration of the stereoisomers of the styrene derivatives was determined by studying the nuclear Overhauser effect in the proton magnetic resonance. The relative stabilities of α-methylthio-β-phenylthiostyrene isomers were determined by equilibrating with the aid of hydrogen chloride at various temperatures.

Additional Evidence for Kinetic Salt Effects upon Chlorinations in Acetic Acid

In the preceding report data were presented which demonstrated an ionic strength influence upon the room temperature chlorination of both alkene double bonds and arenesulfenyl chlorides in anhydrous acetic acid as the solvent (4). The observed kinetic acceleration exerted by the diverse electrolyte was assigIled to the activities of the free (dissociated) ions from the electrolyte and not to the ion pairs. The present communication cites very recent kinetic results involving the chlorination of aromatic hydrocarbons (2) which exhibit electrolytic effects like those found in the arenesulfenyl chlorides. Phenanthrene and biphenyl undergo chlorination in anhydrous acetic acid at 25°C to yield dichloro and acetoxychloro products (2). These second order processes have been interpreted by de la Mare, et v1., to require a sis-addition to the carbon-carbon bond and an ion pair transition state. Qualitative support for an ionic or strongly polar mechanism comes from the increased reaction rate in the presence of the added electrolytes: LiCl; LiC104; NaOAc; and HC104. Two instances for which sufficient data are available for the reaction in the presence of low concentrations of added electrolytes are biphenyl with perchloric acid and phenanthrene with lithium perchlorate. The rate

Kinetic Salt Effects upon Chlorinations in Anhydrous Acetic Acid as the Solvent

Chlorination reactions in anhydrous or glacial acetic acid as the solvent occur at room temperature through the combination of the soft acid, C12, with various soft bases: linear pentenes (10); methyl transcinnamate (3); and 4-substituted arenesulfenyl chlorides (5). The kinetics for the normal chlorinations involve a first order dependence upon the halogen and on the soft base, and in each case the proposed mechanisms postulate ionic chlorine-containing species as the intermediate. The overall process can be formalized by equation 1.