72 KANSAS ACADEMY OF SCIENCE. 



sembling aniline, a property described by Laar^ as belonging to the 

 aniline salt of sulfanilic acid ; although this salt was formed from 

 the corresponding salt of phenylsulfaminic acid by heating, as the 

 following work will show : 



The crystalline precipitate, from which all free aniline and alkyl- 

 ated aniline had been removed, was treated with a solution of caustic 

 potash, yielding an oil which was diazotized. No crystals of j9-nitro- 

 Bodiethylaniline were observed, but ethylphenylnitrosamine was ob- 

 tained. The alkaline solution, which had been freed from aniline 

 and alkylated aniline contained as a base in the salt, was acidified 

 with hydrochloric acid and boiled about fifteen minutes. After cool- 

 ing it was neutralized with caustic soda, and yielded aniline, which 

 was converted into diazo-amido-benzene. 



These experiments prove two points : 



I. Aniline is alkylated by ethyl chlorsulfonate. 

 II. The ethylaniline salt of phenylsulfaminic acid is formed. 



I have previously shown ^ that while sulfuryl chloride dissociates 

 readily into SO2 and CI2, forming with sodium alcoholates large quan- 

 tities of sodium sulfite, ethyl chlorsulfonate does not thus disso- 

 ciate, but unites quantitatively with sodium alcoholates to form 

 addition products, thus : 



which may be broken down in one way (by water), forming R0^—S02 

 — OC2H5+NaCl, and also in another way (by heat), forming NaO — 

 SO2 — OIH-C2H5CI, no sulfite whatever being formed. 



It is, therefore, quite evident that both sulfuryl chloride and 

 ethyl chlorsulfonate behave in a perfectly analogous manner toward 

 aniline ; ^. e., sulfuryl chloride dissociates and acts upon aniline as a 

 chlorinating agent, while ethyl chlorsulfonate is not dissociated, 

 but reacts additively, thus : 



CoHr-O CI CoIJ.O CI 



\ / \ / 



S + H-NH-CeHs [> S-OH 



// \ - // \ 



00 O NII-CeHs 



This addition product then reacts further with aniline, in a man- 



5. J. priikt. Chem., (2), 20, 249 (1879). 



6. Amer. Cheni. Jour., XXX. 212-224 (1903). 



