Drushel and Bancroft — Aliphatic Alcohols. 371 



Art. XXXII. — On the Preparation and Hydrolysis of Esters 

 Derived from the Substituted Aliphatic Alcohols; bj W. A. 

 Drushp:l and G. R. Bancroft. 



[Contribations from the Kent Chemical Laboratory of Yale Univ.— ccxciii.] 



In 1894 de Hemptinne,^ working under tlie direction of 

 Yan't Hoff, determined the velocity constants for the hydrol- 

 ysis of eleven of the lower aliphatic esters. These included 

 methyl, ethyl, propyl acetates, propionates, butyrates, also ethyl 

 isobutyrate and ethyl valerate. This work of deHemptinne 

 showed that the unsubstituted alcohol radical has very little 

 injiuence upon the rate of acid hydrolysis. Later in the same 

 year L5wenherz,t also under Yan't Hoff, determined the veloc- 

 ity constants for the acetates of glycerol and phenol. By a com- 

 parison of these results with those obtained by deHemptinne 

 for methyl, ethyl, and propyl acetates, it was shown that 

 although the alcohol radical has little influence in determining 

 the rate of hydrolysis, its chemical nature is of considerable 

 importance. 



In 1897 and 1898 Geitel;}: studied the velocities of the hydrol- 

 ysis of mono-, di-, and triacetates of glycerol when catalyzed with 

 decinormal hydrochloric acid at 25° and found them to be in 

 the ratios of 1 : 2 : 3. In 1907 Julius Meyer§ investigated the 

 reaction velocity of the hydrolysis of ethylene glycol monoace- 

 tate and diacetate, working at 25*2° and catalyzing the reaction 

 with :N'/50 and JN'/lOO hydrochloric acid. 



The reaction with the glycol diacetate was found to proceed 

 in two stages, the monoacetate being formed as an intermediate 

 product, and this finally decomposing forms ethylene glycol. 

 The rate of hydrolysis in the first stage was determined to be 

 double that of the second stage. E. Abel|| and R. Kremann^f 

 also have studied the acid and alkaline hydrolysis of esters of 

 the polyhydric alcohols. Their results seem to agree with those 

 of Geitel in that they found the rate of hydrolysis in the case 

 of tri-, di-, and monoacetates of glycerol to be in the ratio of 

 3:2:1. 



In 1910 a study of the effect of constitution on the rate of 

 ester hydrolysis was begun in Kent Chemical Laboratory of 

 Yale University. A series of articles^"^ dealing with the hydrol- 

 ysis of esters of substituted aliphatic acids has already 

 appeared. In this paper, and others which may follow, the 

 investigation is concerned with the study of the effect of sub- 



* deHemptinne, Zeitschr. phys. Cham., xiii, 561, 1894. 



f Lowenherz, Zeitschr. phys. Chem., xv, 389, 1894. 



X Geitel, J. pr. Chem. (2). Iv, 417-429, 1897. Ibid. (2), Ivii, 113-131, 1898. 



§ Meyer, Zeitschr. Elektrochem., xiii. 186, 1907. 



II Abel, Zeitschr. phys. Chem., Ivi, 558, 1906. 



IfKremann. Zeitschr. Electrochem., xiii, 307, 1907. 



** Drushel and Hill, this Journal, xxx, 72-78, 1910. 



Am. Jour. Sci. — Fourth Series, Vol. XLIV, No. 263. — November, 1917^ 

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