646 W. A. Drushel — Simple and Mixed Alkyl Phosphates. 



R,R'P0 4 + HOH + HC1 -> HRRP0 4 + ROH + HC1 (also 

 R 2 R'PO ; + HOH + HC1 -> HR a P0 4 + ROH + HC1), (First 

 stage); similarly for the second and final stages. In each case 

 the first alkyl group is hydrolyzed off more easily than the second 

 and third groups, which is in agreement with Lossen and 

 Kohler's observation for the saponification of these esters by 

 barium hydroxide at room temperature. 



Table II. 

 Barium salts of dialkyl phosphoric acids prepared and analyzed for barium. 



Esters 





Per cent. 



of barium 



and Salts 





found 



theory 





Ba(Me 2 P0 4 ), 



* 



35-2 



35-;s 



31-2 



35-4 





Ba(Et 3 P0 4 ), 



r 



30-7 









31-3 







Ba(MeEtP0 4 ) 8 



,rl 



34-0 



33-0 



Salt probably contained some 



from 



r 



34-1 





BaMe 4 (P0 4 ),. 



Me 3 EtP0 4 . 



ill 



34-1 



35-4 



calculated for BaMe 4 (P0 4 ),. 



Ba(MePrPOJ, 



,rl 



32-0 



30 6 



Salt probably contained some 



from 



ill 



32-1 





BaMe 4 (P0 4 ),. 



Me 2 PrP0 4 , 



s 



34-1 







from 



si 



28-8 



27-5 



calculated for BaPr 4 (P0 4 ),. 



MePr 2 P0 4 . 



sll 



28-9 





Salt probably contained some 

 BaPr 4 (P0 4 ), 



Ba(EtPrP0 4 ) 2 



s 



31-6 



29-1 



Salt probably contained some 



from 





31-5 





BaEt 4 (P0 4 ) 2 . 



Et,P.P0 4 , 











from 



r 



27"7 





Probably chiefly BaPr 4 (P0 4 ), 



EtPr PO.. 





27-7 





formed. 



*r, Saponification was made at room temperature; s, on the steam bath. 



The acid hydrolysis of the esters recorded in Table III was 

 made in flasks contained in a boiling water bath especially con- 

 structed for the purpose and fitted with a reflux condenser. 

 Decinormal hydrochloric acid was used as the hydrolytic agent 

 and the course of the reaction was followed in the usual way 

 by making titrations with decinormal barium hydroxide, using 

 phenol phthalein as an indicator. In each case weighed amounts 

 of ester were used, making the concentration of ester in the 

 reaction mixture initially decinormal. Since the end-point of 

 the primary hydrolysis stage could not be determined by titra- 

 tion on account of the interference of the secondary and ter- 

 tiary stages, it was calculated in each case from the weight of 

 ester taken. However, since the secondary and tertiary hy- 

 drolysis products form insoluble barium salts, it was possible to 



