Summary
tert-Alkyl chlorides of the structure R-C(CH3)2Cl, where R-methyl, ethyl, tert-butyl, and neo-pentyl, were reacted with a stoichiometric quantity of acetyl sulfate at room temperature in methylene chloride diluent. Reaction conversion was monitored as a function of time using 1H NMR; structure of the sulfonated products was characterized using 1H and 13C NMR. Reactivity toward sulfonation increased with increasing size of the R group. In all cases the structure of the products was the same as would be expected from sulfonation of the olefin which results from dehydrochlorination of the tert-chloride. The observed behavior was consistent with a mechanism involving dehydrochlorination followed by addition of SO3 to yield a zwitterionic intermediate. Depending upon structure, the zwitterion may either eliminate a proton to form one or more isomeric β,γ-unsaturated sulfonic acids, or it may rearrange to form a five-membered γ-sultone. This chemistry, which is particularly useful in the synthesis of ionomers, represents a direct route to alkyl sulfonic acids when the alkyl halide is the natural starting point in the synthesis.
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Storey, R.F., Lee, Y. Sulfonation of chlorine-containing polymers: Sulfonation of various model tert-alkyl chlorides. Polymer Bulletin 24, 165–172 (1990). https://doi.org/10.1007/BF00297313
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DOI: https://doi.org/10.1007/BF00297313