84 KANSAS UNIVERSITY QUARTERLY. 



when heated to 200° but was partly soluble. We have not yet deter- 

 mined whether the substance is ammonium chlorid or whether some 

 of the possible substances have been formed. 



ACTION OF ESTERS AT HIGHER TEMPERATURES. 



Our failure to obtain some amids by the above method might be 

 due to the low temperature at which the reaction must take place, 

 when the ammonia is boiling under ordinary pressure. Therefore, we 

 attempted to get a more rapid and more complete reaction by heating 

 the mixture of the ester and anhydrous ammonia. The esters were 

 each sealed, with about four times their bulk of liquid ammonia, in 

 strong glass tubes. In one series of experiments these were allowed 

 to warm to the temperature of the room, and in a second series they 

 were heated to 60° or 70°. The tubes were kept sealed for at least 

 twelve hours. They were then cooled with boiling ammonia, opened, 

 the ammonia evaporated off, and the residue examined. 



Eight esters, selected as being types of various acids, were treated 

 in this way. Of these, acetic acid ethyl ester gave no definite results. 

 Acetacetic acid ethyl ester formed a mass of crystals which remained 

 for some time after the ammonia was evaporated, but which soon liq- 

 uified on exposure to the air, forming an oily yellow liquid. We have 

 not yet obtained a satisfactory melting-point for these crystals. Some 

 of the crystals were at once sealed in a glass tube, and have been 

 preserved in this way for more than a year. 



Malonic acid ethyl ester formed white crystals of malonamid, iden- 

 tified as such by the melting-point, 170° (Hoff, J. 1875, 528). 



Pelargonic acid ethyl ester formed a soapy mass when treated in 

 this way. From this mass, crystals of pelargonic amid were obtained. 

 The result agrees with that from ammonia at its boiling-point under 

 ordinary pressure. 



Succinic ethyl ester, benzoic ethyl ester, benzoylacetic ethyl ester 

 and ethyl carbonate gave no results. 



In the second series of experiments, in which the tube containing 

 the ester and ammonia was heated to 60° or 70° in a water-bath, six 

 esters were used. Acetic ester gave a product which had the charac- 

 teristic odor of impure acetamid, but we have not yet succeeded in 

 isolating the pure substance. Tartaric acid ester formed the same 

 white crystalline substance that was formed in the cold. 



From benzoic ethyl ester, succinic ethyl ester, valeric ethyl ester 

 and benzoylacetic ethyl ester no results were obtained. 



With only one of the esters tried — malonic acid ethyl ester — have 

 we had better results at higher temperatures than with the mixture of 

 ester and ammonia at the boiling-point of the liquid ammonia. 



