— 135 



unchanged ketone or aldehyde, it will be possible that, besides primary, 

 secondary and even tertiary bases are also formed, as the following 

 example with benzaldehyde shows: — 



/OH 



LC 6 H 6 COH + NH 3 = C 6 H 6 CH( -> C 6 H 5 CH 2 NH 9 



X NH n 



,OH 



H. C 6 H 5 COH + NH 2 CH 2 C 6 H 5 = C 6 H 5 CH< 



III. C 6 H 5 COH + NH(CH 2 C 6 H 5 ) 2 = C g H 5 Ch/ 



-> (C 6 H 5 CH 2 ) 2 NH 



OH 



N(CH 2 C 6 H 5 ) 2 



-> (C 6 H 5 CH 2 ) 3 N. 



This explains Leuckart's observations. Wallach further argues 

 that if the base is withdrawn from the reaction-mixture by adding a 

 suitable free acid, the uniform progress of the reaction will be pro- 

 moted, inasmuch as only primary, or (when salts of the primary base 

 are sufficiently dissociated at the existing temperature) only secondary, 

 or further also only tertiary base will be formed. The hypothesis of 

 the progress of the reaction further permits of the possibility of bringing 

 besides ammonia, substituted primary or secondary bases in the pres-, 

 ence of free formic acid so into reaction with aldehydes and 

 ketones, that new substituted bases are formed. The experiment has 

 confirmed the hypothesis, and has given the following results: — 



i. The reaction can be accomplished practically uniformly by 

 adding free anhydrous formic acid or acetic acid. 



2. It is possible to keep the temperature of the conversion mostly 

 fairly low, and as a consequence the final products obtained are 

 mainly the salts of the bases formed. Only in a few cases, especially 

 with aromatic bases and with menthone, the occurrence of the formyl 

 compound cannot be prevented. 



3. The sphere of application is very large owing to the fact that 

 different aldehydes and ketones can be brought into reaction with 

 different bases. 



In the experimental part of Wallach 's work, a number of such 

 bases produced by the above-mentioned reaction are described: — 



Diethylcarbinamine (C 2 H 5 ) 2 CH • N H 2 from diethyl ketone, 

 ammonium formate, and acetic acid at 165 ; boiling point 90 . 



a-Phenylethylamine C 6 H 5 CH(NH 2 )CH 3 from acetophenone, 

 ammonium formate, and acetic acid, at 155 ; boiling point 186 ; 



