Ryan and Shannon — The Condensation of Aldehydes^ 6fc. 325 



A chlorofonn solution of the ketone reacted with bromine to form a 

 dibromide, which separated from alcohol as colourless, long, silky needles. 

 These melted at IS?"" C, and gave on analysis the following results: — 



0*2 g. substance, treated with sodium and alcohol by Stepanow's method, 

 requiretl 9-9. c.o. of N/^oA-gNOs for the complete precipitation of the 

 bromide, 



corresponding to Br 39'6. 

 C^jgHjgOgBrj requires Br 3 9 '4. 

 The phenylhydrazone of the ketone was formed by the interaction of its 

 components in alcoholic solution. It consisted of light yellow crystals, which 

 melted at 128 -l'^9° C, and gave on analysis : — 



0-1437 g. substance gave 10-0 c.c. nitrogen at 17° C. and 741 m.m., 



corresponding to .N S'Oo. 

 CaiHaPaN", requires N" 8-33. 



2. Piperonylidene-hutyl-acetoacetic Acid. 



CH2O2 . OeHaCH : CH . CO . OH (O.Hg) . COOH. 



The alkaline parent liquid, from which the piperonylidene-butyl-acetone 

 had been separated, was acidified with dilute hydrochloric acid. The yellow 

 solid which was precipitated was redissolved in dilute alkali, and freed from 

 traces of the ketone by extracting the latter with ether. The acid was 

 then reprecipitated by dilute hydrocliloric acid, and was recrystallised a few 

 times from hot alcohol. It melted with effervescence at 184-185° C, and 

 gave on analysis the following results : — 



0-1431 substance gave 0-3468 00^ and 0-0814 H^O, 



corresponding to 66-09 H 6-32. 

 CieUigOj requires 66-21 II 6-21. 



Fiperonylidene-iutyl-acetoacetic acid crystallises from alcohol as long, 

 colourless prisms, which are fairly easily soluble in acetone, acetic ester, 

 chloroform, or benzene. 



3. Anisylidene-butyl-aceioacetic Acid. 

 CH3O . CgH^ . CH : CH . CO . OH (O.Hg) . COOH. 



A mixture of 12 grams of butyl-acetoaeetic ester, 9 grams of anisaldehyde, 

 and 20 c.c. of 12 per cent, caustic soda solution, with 200 c.c. of water, was 

 shaken mechanically for several days. The alkaline mixture was then 

 extracted with ether, and the ether solution was set aside. 



