CHEMICAL AND PHYSICAL PAPERS. 63 



the action of phosphorus pentachloride upon dry potassium ethyl 

 sulphate, as well as with a body prepared by Wilm" by the action of 

 fuming sulphuric acid upon chlorcarbonic ethyl ester, carbon dioxide 

 being liberated. 



M. Midler^ obtained the same compound, together with isethionic 

 acid, by passing ethylene into chlorsulphonic acid. 



It was also obtained by Sandmeyer*^ by the addition of ethyl 

 hypochlorite to sulphur dioxide. 



On passing chlorine gas, free from air, into a solution of sodium 

 bisulphite in ten per cent, aqueous alcohol, I have found that chlor- 

 sulphonic ethyl ester is at first formed rapidly, but is. destroyed as 

 soon as a considerable quantity of hydrochloric acid has been formed. 



Through Claesson's method ^ free ethyl sulphuric acid is now easily 

 accessible, and from this Nef ^" has prepared chlorsulphonic ester by 

 means of phosphorus pentachloride, but I have had difficulty in re- 

 moving the last traces of phosphorus from the ester thus made. 



The chlorsulphonic ethyl ester used in the experiments hereafter 

 described was made from sulphuryl chloride and alcohol by the fol- 

 lowing modification of Behrend's method : ^^ 



Sulphuryl chloride (Kahlbaum's) was put into a distilling flask 

 fitted with a doubly perforated stopper, through which were inserted 

 the stem of a dropping funnel and a glass tube connected with a cal- 

 cium chloride drying tube. The end of the glass tube was drawn out 

 until almost capillary, and dipped below the surface of the sulphuryl 

 chloride. The delivery stem of the distilling flask led to a wash-bot- 

 tle containing water and provided with a safety tube. The wash- 

 bottle was connected with an aspirator, and air was drawn through 

 the liquid for the double purpose of keeping the liquid constantly 

 stirred and of carrying away the extremely irritating fumes. The 

 flask was immersed in a freezing mixture. Absolute alcohol ( a little 

 in excess of one molecule ) was admitted drop by drop from the drop- 

 ping funnel. When all the alcohol was admitted the freezing mixture 

 was removed, but the air current /was maintained about half an hour 

 longer, until the liquid acquired the temperature of the room and be- 

 came perfectly colorless. After standing, two layers may be distin- 

 guished; the lighter and smaller consists mainly of ethyl sulphuric 

 acid, and the heavier of nearly pure chlorsulphonic ester. The lower 

 layer, after washing with cold water, drying with calcium chloride, 

 and distilling under reduced joressure, yields over sixty per cent, of 

 the theoretical quantity of the pure ester. 



I. 0.3372 gram substance gave 0.5528 gram BaS04. 



6. Jr. prak. Cbem. (2) 1, 244 (1870). 9. Jr. prak. Chem. (2) 19, 231 (1879). 



7. Ber. d. chem. Ges. 6, 227 (1873). 10. Liebitr's Annalen 318, 40 ( 1901 ). 



8. B.er. d. chem. Ges. 19, 860 (1886). 11. Jr. prak. Chem. (2) 15, 28 (1877). 



