OP ARTS AND SCIENCES. ^95 



XVI. 



CONTRIBUTION FROM THE CHEMICAL LABORATORY OF 

 CLARK UNIVERSITY, WORCESTER, MASS. 



THE ACTION OF ACETOACETIC ETHER ON QUINONES : 

 SYNTHESIS OF BENZOFURFURAN DERIVATIVES. 



By M. Ikuta. 



Presented by J. V. Nef, October 14, 1891. 



When chloranil is treated with sodium acetoacetic ether, one or two 

 of its chlorine atoms can be replaced by acetoacetic ether groups. 1 he 

 study of the mono- and the di-substitution products obtamed has led 

 to an interesting synthesis of a number of furfuran derivatives. 



Trichlorquinoneacetoacetic Ether, CeClaOaCCsHoOs). 

 10 crams of acetoacetic ether, dissolved in about 100 c.cm. of ben- 

 zine, are converted by means of sodium in the form of fine wire into 

 the sodium salt. To the emulsion thus obtained is slowly added 18 

 grams (1 molecule) of finely powdered chloranil with continual shak- 

 ing The reaction sets in immediately, and the solution becomes col- 

 ored blue, dark green, and finally brown. In order to complete the 

 reaction the mass is either warmed on a water-bath or allowed to stand 

 for several hours. The part insoluble in benzine, which is removed 

 by filtration and repeatedly washed with fresh benzine, is a very 

 bulky resinous mass, not practicable to work up further ; it consists 

 of sodium chloride, the sodium salts of the mono- and the di-substi- 

 tuted acetoacetic ether derivative of chloranil, besides much resinous 



matter * 



The benzine from the clear orange-colored filtrate is then distilled 



* From this portion, by acidifying and extracting with benzine and crystal- 

 lizing from alcohol, a very slight amount of greenish yellow prisms melting at 

 183° soluble in alkalies with blue coloration, and also dark brown needles 

 insoluble in alkalies and melting above 270°, were obtained, but in too small 

 quantity to admit of further study. 



