ACETO ACETIC ESTER 27 



DEMARCAY, E., 1880. 



Bull. Soc. chim. 33, 516-525 and 575-580 and 34, 31-37; J- Chem. 



Soc. 38, 625. 



Tetric and Oxytetric Acids and their Homologues. 



Methyl-acetoacetic ester when treated with bromin forms two com- 

 pounds, CH 3 CO C (CH 3 ) Br CO 2 C 2 H 5 and CH 2 Br CO C (CH 3 ) 

 Br CO 2 C 2 H 5 . If these are allowed to stand they form CH 3 CO C 

 (CH 3 ) Br H and CH 2 Br CO C (CH 3 ) Br H, but if treated with 

 alcoholic potash they form tetric, 3 C 4 H 4 O 2 + H 2 O, and pxytetric acids, 

 3 C 4 H 4 O 3 +H 2 O. Three sets of salts of tetric acid are formed, (i) 

 Cu O, C 4 H 4 O 2 ; (2) Ba O, 2 C 4 H 4 O 2 ; (3) 2 M 2 O, 5 C 4 H 4 O 2 . 

 Phosphoric pentachlorid with tetric acid forms C 4 H 4 OC1 2 which when 

 treated with chlorin gives C 4 H 4 C1 4 O. 



In the above manner, from the alkyl substituted acetoacetic esters, 

 the following acids and many of their salts were produced ; pentic, 3 

 C 5 H 6 O 2 -h H 2 O ; hexic, 3 C 6 H 8 O 2 + H 2 O ; heptic, 3 C 7 H IO O 2 + H 2 

 O; oxypentic, 3 C 5 H 6 O 3 + H 2 O ; oxyhexic, 3 C 6 H 8 O 3 + H 2 O ; 

 oxyheptic, 3 C 7 H IO O 3 -f-H 2 O, and isohexic and isoxyhexic. The 

 constitution of these was worked out to be ; 



CH 2 CH 2 CH 2 CH (CH 3 ) 

 CO CO and CO CO etc. 



HOFMANN, OTTO, 1880. 



Ann. Chem. 201, 73-89; Ber. 13. 431. 



Action of Zinc and Allyl lodid on Acetoacetic and Diethyl-aceto- 



acetic Esters. 



The action is the same as with sodium and an alkyl halogen, that is, 

 with acetoacetic ester the mono- and the di-alkyl acetoacetic esters are 

 produced ; C 6 H 9 (C 3 H 5 ) O 3 and C 6 H 8 (C 3 H 5 ) 2 O 3 . when allyl iodid 

 is used. When the diallyl acetoacetic ester is treated with zinc and 

 allyl iodid, diallyl acetic ester, CH (C 3 H 5 ) 2 CO 2 C 2 H 5 is produced. 



