Anions toluenesulfonyl chloride, reaction with

Reaction of the diol with p-toluenesulfonyl chloride in pyridine, however, produced the ditosylate in nearly quantitative yield. SN2 displacements by chloride on neopentyl tosylate, which bears certain structural similarities to the ditosylate precursor of CAMPHOS, have been shown to give good yields of neopentyl chloride. However, when l,2,2-trimethyl-l,3-bis(hydroxymethyl)-cyclopentane ditosylate was allowed to react with sodium chloride in hexa-methylphosphoramide, in an attempt to form the dichloride, only N, A -dimethyl-p-toluenesulfonamide was isolated. Reaction of the ditosylate with lithium chloride in ethoxyethanol was exothermic and HC1 was evolved but the dichloride was not isolated. The isolated product contained at least one oleflnic bond. Similarly, in N, TV-dimethylformamide, lithium chloride and the ditosylate gave a product that decomposed on distillation. Faced with such repeated failures, a dihalide route to CAMPHOS was abandoned in favor of a more direct approach reaction of the ditosylate with diphenylphosphide anion. 

Alkyl chlorides, bromides and iodides can be formed by the reaction of alcohols with p-toluenesulfonyl chloride (or tosyl chloride, abbreviated as TsCl) in the presence of a nitrogen base (e.g. triethylamine or pyridine). The OH group is converted into a tosylate (abbreviated as ROTs), which can be displaced on reaction with CF, BF or I-. The stable tosylate anion is an excellent leaving group (SN1 or SN2 mechanism depending on the nature of the alkyl group, R). 

The other /V tosylsulfoximines can be prepared by the tosylation of N-H sulfoximines with p-toluenesulfonyl chloride in the presence of base,. but the two most useful and general methods are the oxidation of /V tosylsulfilimines with basic hydrogen peroxide, m-chloroperbenzoic acid anion, sodium hypochlorite, or ruthe-nium(VIII) oxide/sodium metaperiodate and the copper powder-promoted reaction of sulfoxides with p-toluenesulfonyl azide Handling, Storage, and Precautions (1) is a highly crystalline compound with no known toxicity and unlimited shelf life. 

LVII cationic surfactants (Fig. 15b) with similar structure to the above-described anionic ones were obtained by the same authors [123]. The first two reaction steps were identical to those shown in Fig. 15a. The LV compounds were first subjected to reaction with p-toluenesulfonyl chloride, which was further reacted with anhydrous trimethylamine in DMF, and the reaction products were converted to the desired chlorides by passing their methanolic solution through an ion-exchange column (packed with the chloride form of Amberlyst 27 resin). Aggregation of the LVII surfactants (which were mixtures of anomers) was studied, and the micellar degrees of dissociation, a, in water at 25°C were determined. 

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