E. W. Dean — Esters of Substituted Aliphatic Acids. 337 







Table II. 









Ester 



Hydrolysis at 0° 



Ethyl 

 Butyrate 



Ethyl 



Iso- 



butyrate 



Ethyl a- 



Oxy- 

 butyrate 



N/101 NaOH 

 Ethyl a-, 

 Oxy-iso- 

 butyrate 



Ethyl (5- 



Oxy- 

 butyrate 



Time 



160 



185 



50 



130 



120 





•79 



(•75) 



6-7 



1-5 



2-5 





•67 



•48 



6-3 



1-8 



2-2 





•68 



•46 



7-1 



1-7 



2-1 





•65 



•46 



5-4 



1-6 



1-9 





•62 



•45 



6-4 



1-6 



1-9 







•46 



5-8 



1-6 



1-9 







•45 



5-7 



1-6 









•49 





1-7 





Average 



-68 



•46 

 •47 



6*2 

 6'5 



1-6 

 1-7 



2-1 



Average 

 (duplicate) 



-71 



2-0 



Table III gives a summary of results from Tables I and II 

 and has in addition some values of affinity constants of acids 

 taken from tables of Landolt, Bornstein & Roth (fourth edi- 

 tion). Figures for ethyl acetate and for ethyl propionate are 

 also tabulated for purposes of comparison. 



Table III. Summary 

 Acid hydrolysis 



Temp. 

 Coefficients 



Ester 10 5 K 10 5 K 10 5 K 



25° 35° 45° 25°-35° 35°-45° 



Ethyl butyrate. 52-1 110- 237 2*09 2-17 

 Ethyl iso-buty- 



rate 39-9 91-4 203 2'31 2-23 



Ethyl a-oxy- 



butyrate 39-8 87"0 195- 2'18 2-24 



Ethyl oxy-iso- 



butyrate 21-0 51-2 112- 2-43 2-19 



Ethyf/3-oxy- 



butyrate 10'7 27'6 64-0 2-57 2*33 



Ethyl acetate . . 64-7 163 374- 2*51 2-29 



Ethyl propionate 71-6 179 406 2-50 2-26 



Alkaline 

 hydrol- 



> ysis 



K (10 5 )k(aff) 



(25°) 

 1-49 



1-44 



10-6 



1-8 

 1-34 



Summary. 



I. When hydrolyzed in acid solution three hydroxy-butyrates 

 were found to have considerably smaller velocities of reaction 

 than the esters of the acids from which they were derived. 



Am. Jour. Sci.— Fourth Series, Vol. XXXVII, No. 220.— April, 1914. 

 24 



