The progress of the rearrangement could be followed easily by the shift of the carbonyl absorption in the infrared spectrum from the thiol ester position (5.95 p in the case of the acetate esters) to the amide position a t about 6.15 p . I n most cases the amide was isolated by direct distillation, the polythioformaldehyde remaining undistilled, m.p. 185-190".L6 The infrared and n.m.r. spectra of the latter were identical with those of an authentic sample.In the presence of base, a typical thiolsulfonate reacts readily and completely with a thiol to form a disulfide and a sulfinic acid salt even a t -86". In the absence of base, fairly rapid reaction occurs, which proceeds only part way, but can be pushed toward completion by use of excess thiol or thiolsulfonate. Steric factors significantly affect reactivity of thiolsulfonates, more so than do electronic effects noted thus far. As ancillary points, gas-liquid chromatography was investigated for qualitative and quantitative analysis of thiols, and a tertiary alkyl thiolsulfonate was synthesized, apparently for the first time.(1) (a) This investigation was supported by the U. S.

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Procedure.-A 1-ml. aliquot of the reaction mixture was pipeted into a 50-ml. volumetric flask containing a 5-ml. aliquot of aqueous sodium hydroxide (20 g. per 100 ml. of water) and the flask was heated for 10 min. on a steam bath. The flask was cooled and 2.3 ml. of concentrated hydrochloric acid was added in portions with intermittent cooling. A 25-ml. aliquot of aqueous ferric chloride solution (>0.5 g. per 300 ml. of water plus several drops of concentrated hydrochloric acid) was added and the flask diluted to the mark with distilled water. The absorption of the solution was then immediately measured with a Klett-Summerson photoelectric colorimeter; the blank solution consisted of a 25-ml. aliquot of the ferric chloride solution diluted to 50 ml. The same ferric chloride solution was used throughout a kinetic run.The recorded time of the aliquot is that of complete drainage of the 1-ml. pipet.The absorbancy (A) reading of the colorimeter is directly proportional to the concentration of the original sodium benzoyl aliphatic hydroxamate. The first-order rate equation then is20 _ log (A -A") = 2353 + lo8

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