324 Proceedings of the Royal Irish Academy. 



iodide and 130 grams of aeetoacetic ester, and the mixture was heated to 

 boiling, under a reflux condenser, until its reaction was neutral. The 

 precipitated sodium iodide was filtered, and the filtrate, after concentration, 

 was mixed with water and extracted with ether. The solvent was evaporated, 

 and tlie residual oil was dried with calcium chloride. It was then distilled, 

 and the fraction wliich boiled above 215° C. was collected apart. On re- 

 distillation the pure ester was obtained as a colourless, oily, sweet-smelling 

 liquid, l3oiling at 225-226° C. The yield of the pure product was about 

 50 per cent, of the theoretical yield. The oil gave on analysis the following 

 results : — 



01898 substance gave 04486 CO, and 01684 HoO, 



corresponding to C 64-46 H 9-85. 



C,„ H,3 O3 requires 64-51 H 9-68. 



B. — Action of Aldehydes on Buiyl-Acetoacetic Ester in the Presence of Alkali. 

 1. Fiperonylidene-lutyl-acetone. 

 CH2O. . O^H^CH : OH . CO . CH^ . GJI,. 



About 5 grams of butyl-acetoacetic ester and 8 grams of piperonal were 

 added to a solution of caustic soda in 100 c.e. of 50 per cent, alcohol. On 

 remaining overnight, at the ordinary temperature, a solid separated. This 

 was filtered and freed by means of boiling alcohol from a residue which 

 consisted of sodium carbonate. Piperonylidene-butyl-acetone separated from 

 the alcohol on cooling. It melted at 75'^ C, and gave on analysis the 

 following results: — 



0-1582 substance gave 0-4243 COg and 0-1052 H^O, 

 corresponding to C 73-14 H 7-38. 

 CisHigOs requires C 7317 H 7-31. 

 Fiperonylidene-hutyl-acetone consists of light yellow prisms, readily soluble 

 in warm alcohol or chloroform, soluble in acetone, ether, benzene, or acetic 

 ester, and sparingly soluble in petroleum ether. 



Its oxime was obtained by heating a dilute alcoholic solution of the 

 ketone with hydroxylamine hydrochloride and sodium carbonate for six 

 hours. The mixture was poured into excess of water and extracted with 

 ether. The oxime separated from the ether as colourless needles, which, 

 when recrystallised from alcohol, melted at 126-127° C, and gave on analysis 

 the following results : — 



0-1025 g. substance gave 5-1 c.c. nitrogen at 17-5° C. and 733 m.m., 

 corresponding to N 5-68. 

 C15H19O3N requires JST 5-36. 



