Phelps, Weed, and Housum — Action of Dry Ammonia. 479 



Aet. XLIY. — The Action of Dry Ammonia upon Ethyl 

 Oxalate; by I. K.\Phelps, L. H. Weed, and C. R. 

 Housum. 



[Contributions from the Kent Chemical Laboratory of Yale Univ. — clxvii.] 



Liebig* states that dry ammonia acts upon ethyl oxalate only 

 with difficulty to form ethyl oxamate and a little oxamide ; 

 and further that the greater part of the ethyl oxalate remains 

 undecomposed. Within our knowledge this is the only state- 

 ment in the literature concerning the action of dry ammonia 

 upon anhydrous ethyl oxalate. This paper records the results of 

 experiments made to show the action both in the cold and at a 

 higher temperature of dry ammonia upon dry ethyl oxalate. 



For this work ethyl oxalate was purified by repeated frac- 

 tional distillations until a product was obtained that boiled 

 within the limits of two-tenths of a degree. For each experi- 

 ment portions of this sample were freshly distilled into a dry 

 flask. Dry ammonia was obtained by boiling concentrated 

 ammonium hydroxide in a flask connected with a return con- 

 denser and leading the ammonia gas obtained in this way 

 through a lime tower. 



To show what effect ammonia might have on ethyl oxalate 

 in absence of water, a qualitative test was made by passing 

 ammonia, prepared as stated above, through a glass tube, into 

 pure ethyl oxalate chilled in a bath of ice and salt. A white 

 precipitate appeared after some minutes in the liquid still 

 chilled in the mixture, but wherever the interior of the tube 

 had been wet with the ethyl oxalate a white precipitate 

 appeared almost immediately. This precipitate proved to be 

 a mixture of ethyl oxamate and oxamide. The crude material 

 obtained was freed from ethyl oxalate and the large mass of 

 oxamide by crystallization from alcohol, and from the remain- 

 ing traces of oxamide by distillation under diminished pressure. 

 The ethyl oxamate separated by distillation in this way was 

 recognized as pure by its melting point — 114 - 5°. It boiled at 

 145° C. under 15 mm pressure. It was found that the ethyl oxam- 

 ate may be quantitatively distilled in vacuo as is shown by the 

 following experiment. A portion of the ester weighing Y'6496 

 grm. was introduced into a Claissen flask of 100 cm3 capacity 

 connected through a rubber stopper for a vacuum distillation 

 with a 100 cm3 flask used as a receiver. The side tube of the 

 Claissen flask was short— 5 - 5 cm — and was connected with 

 another tube of 6 miQ bore of sufficient length to reach well into 

 the bulb of the receiver, the rubber stopper closing the receiver 

 serving also as the connector between the sideneck of the 

 Claissen flask and its extension. 



*Ann. Chem., ix, 129. 



