Sulphonic acid anions, nucleophilicity

Another classic anion reaction is that with bisulphite ion to yield crystalline adducts. The structure of these was long a matter of dispute before it was established that they were indeed salts of sulphonic acids (33), reflecting the greater nucleophilicity of sulphur rather than oxygen in the attacking anion. The effective nucleophile is almost certainly (34) rather than HSO3 (HO + HSO3 H O +... 

ROP is carried out in solution, in the melt, in the bulk or in suspension. The involved mechanism can be ionic (anionic or cationic), coordination-insertion or free-radical polymerization [19].The cationic pol)rmerization is initiated by only two catalysts, trifluoromethane-sulphonic acid and its methyl ester [10, 15]. Initiators such as potassium methoxide, potassium benzoate, zinc stearate, n-, sec-, fer-butyl lithium or 18-crown-6-ether complexes are added for the anionic polymerization to induce a nucleophilic reaction on the carbonyl to lead to an acyl-oxygen link cleavage. According to Jedkinski et al. only the primary alkoxides, such as the first mentioned catalyst, can yield polymers with negligible racemization, transesterification and termination [10]. 

The first anionomer has a sulphate end fimctionality similar to that of heparin. Heparin has been shown to be responsible for the binding of a magnitude of proteins in-vivo (5). To prepare the anionic moiety having sulphonic acid at both chain ends, the PTMC diol was employed as a nucleophile to the electrophilic sulfur trioxide trimethylamine complex, giving the PTMC disulphonate as a product. 

As an alternative to the oxidation of sulphides and sulphoxides (see Chapter 10), sulphones can be prepared by the nucleophilic substitution reaction of the sulphinite anion on haloalkanes. In the absence of a phase-transfer catalyst, the reaction times are generally long and the yields are low, and undesirable O-alkylation of the sulphinite anion competes with S-alkylation. The stoichiometric reaction of the preformed tetra-n-butylammonium salt of 4-toluenesulphinic acid with haloalkanes produces 4-tolyl sulphones in high yield [1], but it has been demonstrated that equally good... 

Polymeric phosphonium salt-bound carboxylate, benzenesulphinate and phenoxide anions have been used in nucleophilic substitution reactions for the synthesis of carboxylic acid esters, sulphones and C/O alkylation of phenols from alkyl halides. The polymeric reagent seems to increase the nucleophilicity of the anions376 and the yields are higher than those for corresponding polymer phase-transfer catalysis (reaction 273). 

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