Addition of other sulfur compounds

Sulfur dioxide reacts with olefins in the presence of radical-forming catalysts to yield polysulfones,52 but cyclic sulfones can be obtained from butadiene, 2,3-dimethylbutadiene, isoprene, and hexadiene under specific conditions 53 

Reaction of acetylene with sulfur trioxide gives 2-oxo-l,l-ethanedisulfonic acid, OHC—CH(S03H)2.59 

Sodium hydrogen sulfite can be added to olefins under pressure but also at a useful rate at atmospheric pressure in the presence of tertiary peroxides.60 The course of the addition depends considerably on the reaction conditions and on the nature of the solvent. Kharasch and his co-workers61 have reviewed the applicability of this reaction in relation to the nature of the olefin and the reaction conditions. a-Nitro olefins add sodium hydrogen sulfite even in aqueous solution at 0°, yielding l-nitroalkane-2-sulfonates. 

Truce in N. Kharasch, Organic Sulfur Compounds, Pergamon Press, Oxford-London-New York, 1961, Vol. 1, p. 112. 

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Addition of other sulfur compounds has been rationalized in terms of the nucleophilic attack by the sulfur center. 

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