W. A. Drushel — Hydrolysis of Esters in Fatty Acids. 29 



most rapidly. Table II shows that both ethyl cyanacetate and 

 ethyl monochloracetate are hydrolyzed much more rapidly 

 than ethyl acetate, and that ethyl monochloracetate is hydro- 

 lyzed more rapidly than ethyl cyanacetate although cyanacetic 

 acid is a stronger acid than monochloracetic acid. This again 

 is the result which may be expected if the ethyl cyanacetate 

 molecules exist partly in polymeric form in aqueous solution. 

 Suspecting the rapid increase in acidity of the ethyl mono- 

 chloracetate solution to be partly due to a decomposition of 

 the ester molecule with the liberation of hydrochloric acid, a 

 portion of the reaction mixture was occasionally titrated with 

 decinormal silver nitrate. No measurable decomposition 



in 









Table I. 













Ethyl cyanacetate 



in N/10 HCl. 







A. At 25° C. 















Ethyl 



acetate 



Ethyl chloracetate 



Ethyl cyanacetate 















I 





II 



T in min. 10 5 K 



T in min 



. 10 5 K 



T in min. 



10 5 K 



T in min. 



10 5 K 



























180 



64*6 



75 



46-0 



120 



10-3 



180 



10-4 



300 



69*3 



1120 



46-1 



1480 



10-4 



420 



10-9 



390 



69-1 



2700 



45-7 



2990 



10-4 



1280 



10-1 



1260 



66'4 



4000 



46-3 



4290 



10-6 



2730 



10-2 



1780 



67*3 



4510 



45-1 



5675 



10-1 



4390 



9-9 



2745 



68-5 



5770 



45-8 



7120 



9-9 



6010 



9-8 



3195 



68-6 

















45'8 





10-3 





10-2 





67-7 









B. At 35° C. 





































61 



159-2 



120 



92-7 



900 



22-4 







120 



158*9 



240 



92-4 



1105 



22-3 







240 



158-8 



360 



92-4 



1300 



24-0 







420 



159-6 



480 



92-4 



1440 



232 







540 



159-3 



1650 



88-5 



2430 



23-3 







715 



159-8 





91-7 



2670 

 3780 



23-2 

 23-0 















159-3 









23*1 







C. At 50° C. 





































5 



491-7 



20 



318-9 



20 



75-0 







20 



496-4 



50 



321-9 



50 



78-0 







35 



498 6 



110 



314-9 



110 



77-4 







50 



501-5 



180 



320-3 



180 



77-1 







80 



500-0 



240 



321-5 



1140 



76-6 







110 



497'2 



300 



329-6 



2970 



76-8 







180 



493-2 





QOl 'O 











IjCl.Q 





496-9 



