No^-EMBER 5, 1909] 



SCIENCE 



623 



stances should be analogous to the catalysis 

 produced by alkalies on the reaction be- 

 tween alkyl halides and acids. According 

 to this theory only the cations formed by 

 the union of the H ion with the amide, 

 oxime, hydrazide, etc., should be appre- 

 ciably hydrolyzed. 



CHaCONHj+H+Ci + H.O ?^ CH.COXHj+Cl+H^O 

 ?=i CH3C00H-|-NH,-|-C1. 



This has been araplj^ verified in this labo- 

 ratory by Mr. Nirdlinger, and here we have 

 a reaction of ions. We are studying, too, 

 the reverse reactions : viz., the formation of 

 amides, hydrazides, etc., by the action of 

 ammonia, amines and hydrazines on the 

 organic acids, esters or acid chlorides, with 

 and without catalyzers, in different sol- 

 vents, etc. We shall study especially the 

 velocity of the reaction and the equilibrium 

 in the gaseous phase. 



In the case of the oxime, in which we 

 have a reversible change as follows : 



(CH3)XO-|-NH30H=± (CH3),C=NH0H 

 ?=♦ (Cn3),C=X0H-|-H, 



Dr. Johnson and Mr. Desha have discovered 

 the first reversible reaction in which the 

 so-called third law of catalysis fails to hold, 

 in which the equilibrium point is changed 

 by a change in the concentration of the 

 catalyzer. 



This theory of acid-catalysis allows us to 

 predict that such cations will be found to 

 react with alcohol, phenols, amines, hydra- 

 zines, etc. Dr. E. E. Reid has been able 

 to show by the necessary quantitative mea.?- 

 urements that the amides react with alco- 

 hols in the presence of acids and form 

 quantitative yields of esters, 



/OR 



CH,CONH,-FHOR ?± CH,C'- NH, 



, \0H 

 ^ CH,COOR-f NH., 



and that excellent yields of esters may be 



obtained also from anilides and hydrazides 

 under the same conditions. This suggests 

 that the ordinary Fischer esterification 

 method for the isolation of amino acids in 

 the form of their esters from casein, horn, 

 hair, polypeptides, etc., might be effectively 

 modified in some cases by boiling the sub- 

 stance in alcoholic hydrochloric acid in- 

 stead of in aqueous solutions. The e.ster 

 would then be formed directly instead of 

 through the present indirect destructive 

 methods. 



NH,CH,CO|NHCri,CO|NHCHXOINHj 

 RO|H Ro|h R0|H 



The chief disadvantage would be the in- 

 solubility of the proteid in the alcohol, but 

 we find that our difficultly soluble com- 

 pounds seem to work well. 



Two other reactions, worked out by Dr. 

 J. M. Johnson in our laboratory, are re- 

 called, the simplest explanation of which is 

 that non-ionized salts are transformed into 

 other products. Acetyl chloraminobenzene 

 and hydrochloric acid react with a velocity 

 proportional to the concentration of the 

 undissociated salt present, or to the square 

 of the concentration of the hydrogen ions. 

 Two other explanations of this reaction are 

 to be considered, but as they are at present 

 very improbable, they will be discussed in 

 a later communication. 



CHjCONClCJInH-H-f-Ci ?± CHjCONHCI.CeF. 

 -^ CH3C0NHC„H,Cl-fH-|-Cl. 



The other reaction is one in which imido- 

 esters of various types yield alkyl halides 

 when heated with halogen hydrides. In 

 this case, too, an undissociated salt seems 

 to be decomposed. 



ROCHa-l-H+Ci ?± R0CH..HC1 -> R0H-|-CH,C1. 



This work disproves the validity of the 

 so-called second law of catalysis, which pos- 

 tulated that there must be direct propor- 

 tionality between the reaction velocity and 



