Substituted Aliphatic Alcohols. • 377 



In alkaline solution the reaction was similar to that described 

 above, and the presence of the aldehyde was shown by warm- 

 ing the solution of hydrolysis products on the steam bath, when 

 there was formed the characteristic aldehyde resin of acetalde- 

 hyde. 



Esters Derived from Beta Substituted Ethyl Alcohols. 



The following esters of this class were studied : 



^-hydroxy ethyl acetate, CH,(0H)CH.^.0.C0.C03, 

 ^-raethoxy-ethyl acetate, Cn^(OCH3).CH.^.O.CO.CH3, 

 ;8-ethoxy-ethyl acetate, CH,(OC^HJ.CH,.0 CO.CH3 

 /3-chlor-ethyl acetate, CH^Cl.CH,.O.CO.CH3, 

 ^-brom-ethyl acetate, CH,Br.CH^.0.C0.CH3. 



These esters were hydrolyzed in decinormal hydrochloric acid 

 at 25°, 35°, and 45°, and measurements made from which the 

 velocity constants were calculated. The hydrochloric acid used 

 as a catalyzing agent was standardized by precipitation with 

 silver nitrate. The titrations were made with decinormal 

 sodium hydroxide, free from carbon dioxide, using phenolphtha- 

 lein as an indicator. 



The hydroxy-, metlioxy-, and ethoxy-ethyl acetates were 

 found to be very soluble in water. The introduction of halo- 

 gen in the /3-position of the ethyl radical of the alcohol gives 

 to the derived ester a much greater insolubility. Only eiglit 

 cubic centimeters of the /3-brom-ethyl acetate could be dissolved 

 in a liter of water. The /5-clilor-ethyl acetate was found to 

 be slightly more soluble. 



In the case of the hydroxy-, methoxy-, and ethoxy-ethyl ace- 

 tates 2'5 cm^ of each ester were dissolved in 250 cm^ decinor- 

 mal hydrochloric acid, previously warmed in the thermostat 

 to the required temperature. As soon as the ester was com- 

 pletely dissolved a 25 cm^ portion of the reaction mixture was 

 withdrawn by means of a pipette, and run into about one hun- 

 dred cubic centimeters of cold distilled water in a 300 cm^ 

 flask. The pipette was allowed to drain thirty seconds and 

 the time was then recorded, and the solution titrated at once 

 with decinormial sodium hydroxide. Subsequent titrations 

 were made at suitable time intervals, and the final measure- 

 ments were taken when a sufficient time had elapsed to insure 

 that the hydrolytic action was complete. To insure uniformity 

 in experimental conditions a sample of ethyl acetate was hydro- 

 lyzed at the same time as the esters of this group, and the 

 hydrolysis of each ester was made in duplicate. 



On account of the greater insolubility of the beta halogen 

 substituted esters only two cubic centimeters of each ester 

 were dissolved in 250 cm^ of decinormal hydrochloric acid. 

 Measurements of the velocity of the hydrolysis of these esters 

 were made as just described. In order to ascertain if any 

 halogen was liberated in the form of free halogen acids derived 



