Halobenzenes, alkylation sulfonation

Many variations of the reaction can be carried out, including halogenation, nitration, and sulfonation. Friedel-Crafts alkylation and acylation reactions, which involve reaction of an aromatic ling with carbocation electrophiles, are particularly useful. They are limited, however, by the fact that the aromatic ring must be at least as reactive as a halobenzene. In addition, polyalkylation and carbocation rearrangements often occur in Friedel-Crafts alkylation. 

Much of the research on the SbCls-catalyzed halogenation of arenes has focused on the chlorination and bromination of perfluoroalkyl-substituted aromatics [14]. The reaction of organic disulfides with electron-rich aromatic compounds under catalysis with SbCls and AgSbFg affords unsymmetrical aryl sulfides in modest yields [15a]. Electrophilic sulfinylation and sulfonation can be similarly effected by SbCls [15a-c]. Alkyl- and halobenzenes give thiocyano derivatives when treated with a mixture of SbCls and Pb(SCN)2 in CCI4 [16],... 

Uses. Tetramethylene sulfone has high solvent power for aromatics and has been used extensively by Olah and co-workers for Friedel-Crafts type nitrations and for studies of the mechanism of nitronium tetrafluoroborate nitration of alkyl-benzenes and halobenzenes in homogeneous solution. It is a superior solvent for quaternization of tertiary amines with alkyl halides, since it has a high dielectric constant and does not enter into side reactions observed with nitrobenzene and dimethylformamide. For example in the synthesis of the acridizinium salt (3), Bradsher and Parham effected quaternization of (1) with benzyl bromide in tetramethylene sulfone at room temperature in excellent yield. Several other salts analagous to (2) were obtained in good yield and in crystalline form with use of tetramethylene sulfone, whereas with other solvents the products were colored... 

Studies by Kiersznicki and co-workers demonstrated that chlorosulfonic acid is an effective catalyst in the alkylation of arenes by reaction with alkenes. Benzene, toluene and ethylbenzene were alkylated by propene, elhene and 2-butene in the presence of chlorosulfonic acid which strongly catalysed the alkylations and inhibited polyalkylation. Increasing the concentration of the catalyst enhanced the proportion of /7-isomers in the products. Fluoro-, chloro-and bromobenzenes were similarly alkylated by reaction with C2-C4 alkenes using chlorosulfonic acid as catalyst. The optimum alkylation conditions were with a halobenzene alkene ratio of 1 0.25, a catalyst concentration of 0.33 mol mol" of fluorobenzene and 0.5 mol mol of the other halobenzenes, a temperature of 70 C and a reaction time of 2 hours. Alkylation with propene gave haloisopropylbenzenes the monoalkyl products were obtained as o-, m- and p- mixtures, the relative amounts depended on the quantity of catalyst used and the by-products were dialkyl derivatives, sulfonic acids and sulfones. In the reaction of benzene with propene, fluorosulfonic acid was a more potent alkylation catalyst than chlorosulfonic acid. ... 

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