62 KANSAS ACADEMY OF SCIENCE. 



ON THE ALKYL SULPHATES. 



By F. W. BusHONG, Kansas City University. 

 Read before the Academy, at Topeka, January 1, 1903. 



TWO lowest members of the series of neutral alkyl sulpliates, 

 dimethyl sulphate and diethyl sulphate, have long been known. 

 In 1870 Chapman ^ obtained impure diisoamyl sulphate by passing 

 sulpur dioxide into isoamyl nitrite. Stempnewsky^ states that alkyl 

 sulphates are formed by the interaction of silver sulphate with alkyl 

 haloids, but Nef ^ found that while this method yields normal dipropyl 

 sulphate and diisoamyl sulphate it does not furni,sh diisopropyl sul- 

 phate nor diisobutyl sulphate, and accounts for this by pointing out 

 that these esters possess very low dissociation points. On this ac- 

 count, he suggests that the only possible method which presents itself 

 for their synthesis at low temperature is the interaction of sulphury 1 

 chloride or its esters with alcoholates. 



Following this suggestion, I have prej)ared ethyl isopropyl sulphate, 

 ethyl isobutyl sulphate and ethel isoamyl sulphate from chlorsulphonic 

 ethyl ester and sodium alcoholates, and diisopropyl, diisobutyl and 

 diisoamyl sulphates from sulphuryl chloride ^d the sodium alcohol- 

 ates. 



The reaction between sulphuryl chloride and sodium alcoholates is 

 complicated and the yield of alkyl sulphate cut down by the dissocia- 

 tion of the sulphuryl chloride into suli^hur dioxide and chlorine. I 

 wish, on this account, to investigate this reaction further before stating 

 ray results, and at present describe only my experiments with chlor- 

 sulphonic ethyl ester, 



CHLORSULPHONIC ETHYL ESTER, ITS PREPARATION AND PROPERTIES. 



Soon after the constitution of sulphuric acid and its relation to 

 chlorsulphonic acid and to sulphuryl chloride had been established, 

 R. Williamson^ prepared chlorsulphonic ethyl ester "by direct com- 

 bination of chloride of ethyl with anhydrous sulphuric acid. Its 

 composition was determined by finding the weight of the product ob- 

 tained by combining a known weight of SO3 with chloride of ethyl." 



Purgold"^ found that in this reaction at least two of the three possi- 

 ble isomers are formed, and his work has, in part, been confirmed by 

 Armstrong.'' He also proved that the ester thus obtained is identical 

 with the chloranhydride of ethyl sulphuric acid, which he made by 



1. Ber. d. chem. Qes. 8, 920 (1870). 3. Liebig's Annalen 318, 40 (1901). 



2. Ber. d. chem. Qes. 11, 514 (1878). 4. Jr. Chem. Soc. 10, 100 (1857). 

 5. Leibig's Annalen 149, 124 (1869), Ber. d. chem. Ges. 6, 502 (1873). 



