W. A. Drushel — Simple and Mixed Alkyl Phosphates. 645 







T 



\BLE I. 









Boiling 



Pressure 



,— Density — , 



Solubility in 



Esters 



point 



in mm. 



0° 



22° 



water at 25° 



Me,P0 4 ** 



197 



760 



1-218 



1-200 



1 : 1 



Et,'P0 4 



215 



760 



1-071 



1-056 



1 : 1 



Pr a P0 4 



131 



15 



1-025 



1-007 



1 : 155 



Isobu 3 P0 4 



152 



15 



0-978 



0-965 



1 : over 1000 



Me 2 EtP0 4 



203 



760 



1-176 



1-161 



1 : 1 



Me 2 PrPO 



116 



15 



1-195 



1-180 



1 : 1 



MePr.PO 



129 



20 



1-077 



1-059 



1 : 22 



Et 2 PrP0 4 



130 



20 



1-098 



1-077 



1 : 1 



EtPr PO, 



145 



20 



1-046 



1-025 



1 : 45 



** Me denotes methyl ; Et, ethyl, etc. 



ing salts agrees well with the calculated amount, and that 

 when barium hydroxide under the same conditions acts upon 

 mixed alkyl phosphates in no case does the amount of barium 

 found in the resulting salts agree with the amount calculated 

 for the theory that only one of the two different alkyl groups 

 is hydrolyzed off to the exclusion of the other. It is safe to 

 conclude, contrary to Lossen and Kohler's theory, that in 

 mixed alkyl phosphates barium hydroxide does not remove 

 one of the different alkyl groups to the exclusion of the other 

 and that, although one alkyl group may he more readily 

 attacked than the other of two different alkyl groups, the reac- 

 tion does not by any means go wholly in that direction. 



The reactions involved in the preparation and hydrolysis of 

 alkyl phosphates may be briefly summed up in the following 

 equations, where R denotes an alkyl group and R' a different 

 alkyl group : 



2ROH + 2Na -> 2RONa + H„ 



3RONa + POCl 3 -> R,P0 4 + 3NaCl, 



2R 3 P0 4 + Ba0 2 H, -> BaR 4 (P0 4 ) 2 + 2ROH, 



(also to a very slight extent, R 3 P0 4 + BaO„H 2 -^ BaRPO * + 



2ROH), 

 BaR 4 (P0 4 ) 2 + H 2 S0 4 -> 2HRP0 4 + BaS0 4 , 

 2HR„P0 4 + Ag,0 -» 2Ai?R 2 P0 4 + H 2 0, 

 AoR;P0 4 + R'l -> R,R'P0 4 + Ao-I, 

 2R 2 R'P0 4 + Ba0 2 II 2 ^ BaR 2 R' 2 (P0 4 ) 2 + 2H,0, 

 also 2R 2 R'P0 4 + Ba0 2 H 2 -> BaR 4 (P0 4 ) 2 + 2H 2 0. 

 R 3 P0 4 + HOH + HC1 -> HR 2 P0 4 + ROH + HC1 (First 



stage), 

 IIR 2 P0 4 + HOH + HC1 -> H 2 RP0 4 + ROH + HC1 (Second 



stage), 

 H 2 RP0 4 + HOH + IIC1 -> H 3 P0 4 + ROH + HC1 (Final 



stage). 



* This salt being insoluble is readily removed by filtration. 



