BARTOW AND MCPARLAND : LIQUID AMMONIA. 81 



melt at 200 ', but which turned red when heated or allowed to stand 

 for some days. No amid was isolated. The only other chlorids tried 

 in this way were benzoyl chlorid and sulfuryl chlorid. From these 

 benzamid and sulfamid were obtained. 



The chief drawback in the above method is the difficulty of freeing 

 the amid from the ammonium chlorid which is formed at the same 

 time. Up to this time we have been prevented from further experi- 

 ments with chlorids by our lack of pure specimens. When such 

 specimens are secured, the experiments will be continued. 



ACTION OF LIQUID AMMONIA ON ESTERS. 



Since the action of aqueous and alcoholic ammonia on esters of or- 

 ganic acids will cause the formation of amids, sometimes even in the 

 cold, a series of experiments with liquid ammonia and the esters 

 promised good results. The expected reaction is as follows : 

 KCOOC -H, + NH3 = RCONH2 + CiHsOH 



for the ethyl esters, and, more general, 



KCOOR'+ NH3==RCONH2+ R'OH. 



Authorities differ as to the effect of alcohol on amid synthesis. 

 One (Bonz, Ph. Ch. 2, 900) says free alcohol must not be present. 

 Another uses alcoholic ammonia in the synthesis. It would seem to 

 us that no general statement should be made, since, in some of our 

 experiments, we easily obtained well-crystallized products, while in 

 others no crystals were obtained ; possibly because of the alcohol 

 formed by the reaction. 



The method of procedure was similar to that used with chlorids. 

 The ester was dropped into the liquid ammonia contained in a small 

 crystallizing dish insulated by cotton. A large excess of ammonia 

 was used — from six to ten times the bulk of the esters. The dish was 

 covered with a ground-glass plate and allowed to stand until the am- 

 monia was all evaporated. When a crystalline residue was obtained, 

 i,t was dried on a porous plate and a melting-point determination 

 made. The reaction between the esters and the ammonia is not vio- 

 lent, as when chlorids are used, so that when crystals can be ob- 

 tained the method is much better than the chlorid method. 



Forty-two esters have been treated in this way. From nine of 

 them, crystallized compounds were obtained which had melting- 

 points corresponding to the melting-points given for the respective 

 amids in the literature on the subject. Two gave compounds with 

 higher melting-points, and seven gave products, with high melting- 

 points, that were probably decomposition products. The remainder 

 were apparently not acted upon. 



The first esters tried were those of the chloracetic acids. These 



