ACETO ACETIC ESTER 1)5 



CONRAD, M. AND L. LIMPACH, 1891. 



Ber. 24, 2990-2992, J. Chem. Soc. 62, 78. 



Synthesis of Quinolin Derivatives by means of Alkyl Acetoacetic 



Esters. 



Methyl-acetoacetic methyl ester and anilin, when mixed and allowed 

 to stand, form phenyl-amido-methyl-crotonic methyl ester. By quickly 

 heating this, it is changed into dimethyl-hydroxyquinolin, C9 NH4 

 (CH3)20H, [(CH3),:OH = 2':3':4']. Methyl-ethyl-hydroxy-quin- 

 olin is produced similarly from phenyl-amido-ethyl-crotonic methyl 

 ester. 



NEF, J. U., 1891 



Ann. Chem. 266, 52-138; J. Chem. Soc. 62, 140. 



Acetoacetic Ester. 



A large number of experiments are performed relative to determining 

 the constitution of acetoacetic ester and the position of the sodium in 

 the sodium derivative, and the conclusions drawn are that acetoacetic 

 ester is not a ketone but is represented by CH3 COH : CHCO2 C2 H5 

 and that in the sodium derivative the sodium is joined to oxygen. If 

 by heating the sodacetoacetic ester with an alkyl halogen the alkyl is 

 substituted for the sodium, the reaction should be more energetic if the 

 heavier metals, such as copper or lead, be in the acetoacetic ester in 

 place of sodium, but solutions of the copper or lead derivatives of aceto- 

 acetic ester do not react with ethyl iodid at ordinary temperatures — 

 which proves that no direct substitution of the metal takes place. The 

 author supposes an intermediate addition product to be formed with 

 an alkyl iodid, for example, with benzylchlorid, CH3 CONaClCH 

 (CH2C6H5)C02R is first formed and then HCl spHts off leaving 

 CHsCONa : C (CH.X6H5) CO^R and by continued action CH3CONaClC 

 (CH2 Cfi Hs)^ CO2 R and then CH3 COC (CH^ C^n,), CO^ R are formed. 

 As proof of the existence of hydroxyl in acetoacetic ester its acid 

 properties and its behavior towards phenyl hydrazin, ammonia and 

 the amids are mentioned, also the fact that acetoacetic ester and 

 its mono-alkyl derivatives are not reduced by treatment with sodium 

 in ethereal solution while the diethyl derivative is converted into 



