Ryan and Algar — On Unsaturated fi- Diketones . — II. 13 



substance melting at 111° 0. is therefore ethyl-7-emnanienyl-isoxazole-a- 

 carboxylate, and is probably formed in the following manner : — Excess of 

 hydroxylamine hydrochloride, when boiled with the methyl ester in an ethyl 

 alcohol solution, is converted into the isoxazole of the acid, which is 

 simultaneously esterified to the ethyl ester. 



The compound which melts at 111° C. was boiled with potash until it had 

 all dissolved ; and the solution was acidified with hydrochloric acid. The 

 white solid which was precipitated was filtered and re-crystallized from dilute 

 alcohol. This compound melted at 190°-192°C, and on analysis gave the 

 following results : — 



0T454 grm. of substance gave 0-3583 grm. C0 2 and 0-0601 grm. H 2 0, cor- 

 responding to C 67'2, H 4-59. Also, 0-1745 grm. substance gave 104 c.c. N at 

 4-5° C. and 756 mm. pressure, corresponding to N 7 - 00. 



C 6 H 5 . CH : CH . C . CH : C . COOH requires C 67-0, H 4'2, and N 6-51. 



II i 



N O 



Methyl-y-cinnamenyl-isoxazole-a-carboxylate was obtained in a later 

 preparation when methyl alcohol was used as a solvent instead of ethyl 

 alcohol. This compound crystallizes from dilute alcohol in long colourless 

 needles, which melt at 142°-143° C. 



0-1959 grm. of the substance gave 0-0878 grm. H 2 0, and 0-4881 grm. C0 2 , 

 corresponding to C 67-95, H 4-97. 



CHnNOj requires C 68-1, H 484. 



Methyl-a-(3-Dibromo-(3-phenyl-propionyl-pyruvate, 

 C 6 H 5 . CH Br . CH Br . CO . CH 2 . CO . COOCH 3 . 



2-32 grms. of methyl cinnamyl-pyruvate were dissolved in 5 c.cs. chloro- 

 form, and a solution of l - 6 grms. of bromine in 5 c.cs. chloroform was added 

 slowly. The red colour of the bromine disappeared immediately ; and no 

 hydrobromic acid was evolved. On evaporation of the chloroform in vacuo an 

 oily residue was obtained, which was crystallized by dissolving in hot benzene 

 and precipitating by addition of ligroin. It melted at 134° C. to a red liquid. 



This compound crystallizes in nearly colourless prisms, which are insoluble 

 in water, sparingly soluble in ligroin, soluble in carbon disulphide or ether, 

 and readily soluble in chloroform or benzene. When warmed with dilute 

 aqueous potash, it undergoes ketonic hydrolysis. Its alcoholic solution gives a 

 bright red colour with ferric chloride. 



0-1991 grm. of substance gave 0-2945 grm. of C0 2 and 0-0593 grm. H a O, 

 corresponding to C 40-3, H 3-3. 



C ls H 12 Br 2 4 requires C 39-8, H 31. 



