72 Drusfiel and Hill — Esters of Halogen Substituted Acids. 



Art. VI. — Hydrolysis of Esters of Halogen Substituted 

 Acids ; by W. A. Drushel and J. W. Hill. 



[Contributions from the Kent Chemical Laboratory of Yale Univ. — ecxii.] 



1. Acetic Esters. 



A GREAT deal of attention has been given by chemists in 

 recent years to the study of the velocity of liydrolysis of 

 esters. Among others, acetic esters have been liydrolyzed 

 under various conditions and the velocity of this reaction 

 measured. In 1883 W. Ostwald* published the results of his 

 experiments in determining the strength of different acids as 

 shown by their catalytic action on the hydrolysis of methyl 

 acetate. Later deHemptinne,f working under the direction of 

 Yan't Hoff, determined the rate of hydrolysis of a large num- 

 ber of esters, among them methyl, ethyl and propyl acetates. 

 Lowenherz;]; later took up the subject and included in liis 

 studies the methyl and ethyl esters of chloracetic acid and the 

 ethyl di- and tri-chloracetates. Since then Price § has done 

 some work in the same held, adding isobutyl acetate to the list 

 of esters whose rates of hydrolysis have been measured. All 

 of these investigators, with the exception of Ostwald, used 

 hj'drochloric acid as a catalyzer to aid the hydrolytic action 

 of water. YanLaar|| determined the reaction when water 

 alone was present. 



The present work was undertaken to extend our knowledge 

 of the effect on the rate of hydrolysis when the various halo- 

 gens are substituted for hydrogen in the acetyl end of the 

 ester molecule; It has been shown by Stentor,^[ Buchanan,** 

 Kastle and Keiser,f f and others,;}::}: that the halogen substituted 

 acids react with water and their sodium salts with water and 

 sodium hydroxide, with the splitting out of the halogen and 

 substitution of hydroxyl according to the equations : 



C1-CH,C00H + HOH= HOC H^COOH + HCl 

 Cl-CH,COONa + HOH=HOCH,COONa + HCl. 



Apparently no one with the exception of Lowenherz has 

 investigated the behavior of the esters of the halogen sub- 

 stituted acids. 



*J. prakt. Chem. (2), xxviii, 449. §Abs. Chem. Soc. (Lon.), xi, 528. 



■fZeitsehr. phys. Chem., xiii, 561. | Zeitschr. phys. Chem,, xiii, 736. 



jZeitschr. phys. Chem., xv, 397. 



1[Proc. Chem. Soc, 1909, 236; Trans. Chem. Soc, 1907, 460. 



**Ber. Dtsch. Chem. Ges., iv, 340, 1871. 



•ft Amer. Chem. Journal, xv, 471. 



X\ Slator, Trans. Chem. Soc, 1904, 85 and 1291 ; 1905, 481. 



