376 Drushel and Bancroft — Esters Derived from the 



of Ladenburg.* This ester was analyzed for halogen as a fur- 

 ther test of the purity of the substance. 



Chlorine found, I. 28 '40,^, II. 28'18^ III. 28-34^. 

 Chlorine calculated, 28 '94^. 



The /5-brom-ethyl acetate was obtained by the method of 

 Louis Henry,f which is essentially the same as that described 

 by De Mole,:}; who treated his monacetin of ethylene glycol with 

 hydrobromic acid to obtain this ester. Ethylene glycol diace- 

 tate was saturated with dry hydrobromic acid gas, and the 

 resulting product was fractionated. The boiling-point and spe- 

 cific gravity of the purified ester corresponded to the values 

 given in the literature. The halogen content of the ester was 

 also determined by analysis. 



Bromide found, I. 47-50^, II. 47'56,^, III. 47*50^. 

 Bromine calculated, 47'86^. 



JEJydrolysis of Esters. 



Esters Derived from Alpha Substituted Ethyl Alcohols. 



The following esters of this class were studed : 



a-chlor-ethyl acetate, CH3.CHCI.O.CO.CH3. 

 a-ethoxy-ethyl acetate, CH,.CH(OC„HJ.O.CO.CH,. 

 a-chlor-ethyl propionate, CH3.CHChO.CO.CH^.CH3. 



These esters are found to be unstable compounds, which are 

 decomposed immediately upon dissolving in decinormal hydro- 

 chloric acid. This was shown by dissolving 2-5 cm^ of the 

 a-chlor-ethyl acetate in 250 cm^ of the standard decinormal 

 hydrochloric acid. On titrating 25 cm^ of this reaction mix- 

 ture with decinormal sodium hydroxide, the initial titration 

 required considerably over 45 cm^, and the titration made after 

 allowing the reaction mixture to remain in the thermostat for 

 ten days showed an increase of only one to two cubic centi- 

 meters. This increase was accounted for by the more complete 

 splitting out of halogen, which was shown by titrating with 

 silver nitrate. 



In the case of the a-chlor-ethyl acetate the hydrolysis pi-o- 

 ducts were acetaldehyde, acetic acid and hydrochloric acid, 

 while the a-chlor-ethyl propionate gave acetaldehyde, propionic 

 acid, and hydrochloric acid. The a-ethoxy-ethyl acetate gave 

 a similar result yielding acetaldehyde, ethyl alcohol and acetic 

 acid. The presence of the aldehyde was shown in each case 

 by treating a portion of Schiff's reagent with a few drops of 

 the solution of the hydrolyzed ester, which at once imparted a 

 deep reddish violet color to the solution. 



*Ladenburg, ihid., xvi, 1407-1408, 1883. Jaliresb. 1883, 591. 

 f Henrv, Rec. d. trav. chim. d. Pays-Bas. xxi, 243-254, 1901. Bull. Acad. 

 Eov. Belg. cl. sci. (3), xxxvii, 236-248, 1901. 

 f De Mole, Ann. d. Cliem., clxxii, 12]. 1874. 



