ACETO ACETIC ESTER I I I 



SCHONBRODT, R., 1889. 



Ann. Chem. 253, 168-205 ; J. Chem. Soc. 58, 27 ; Ber. 22, 680 (C). 



Derivatives of Acetoacetic Ester. 



By passing chlorin through cupracetoacetic ester in chloroform the 

 mono- and di-chlor derivatives were formed and the corresponding 

 bromin derivatives were similarly formed. lodacetoacetic ester pro- 

 duced from cupracetoacetic ester and iodin is an unstable oil which 

 decomposes at 25° in a vacuum, its specific gravity is 1.705 at 14°, in 

 alcoholic solution it gives a blood red color with ferric chlorid. Silver 

 chlorid converts it into mono-chlor-acetoacetic ester. When treated 

 with silver nitrite an oil is produced which gives a blood red color with 

 ferric chlorid and sulfuric acid and which is probably nitroacetoacetic 

 ester. Treated with phenylhydrazin it gives phenyl-methyl-nitroso- 

 pyrazolone [ i : 3 : 4 : 5] . Sodacetoacetic ester and lodacetoacetic ester 

 give diacetosuccinic ester. lodacetoacetic ester and metallic silver give 

 CH3 COCCO, R 



diacetofumaric ester, r^r\nr^n> r>- Cupracetoacetic ester boiled in 



Crl-j CCJCCU2 K. 



benzene with sulfur gives thioacetoacetic ester. In presence of alcohol, 



phosphorus acts on cupracetoacetic ester to form acetoacetic ester and 



tri-ethyl phosphite, P (OC2 1^5)3. Cupracetoacetic ester and arsenic 



trichlorid form cuprous chlorid, arsenic and mono-chlor-acetoacetic 



ester. Unsuccessful attempts were made to replace hydrogen by copper 



in methyl-acetoacetic ester. 



GABRIEL, S. AND J. HAUSMANN, 1889. 



Ber. 22, 2017-2019 ; J. Chem. Soc. 56, 1172. 



Action of Orthocyanobenzylclilorid on Sodacetoacetic Ester. 



In this reaction two products are formed, a small amount of di-ortho- 

 cyanobenzylacetoacetic ester, CH3 COC (CNCe H^ CH^^ CO^ C, H5 . 

 and a much larger amount of orthocyanobenzylacetic ester, or ortho- 

 cyanohydro-cinnamic ester, (CNCe H^ CH^) CH^ CO^ C^ H5. The latter 

 is a colorless, crystalline substance melting at gS'-gg" which is decom- 

 posed when warmed with hydrochloric acid into a-hydrindone, carbon 



CO 

 dioxid, alcohol and ammonia. a-Hydrindone. C6 H4 <pTT > CH2, 



crj'Stallizes and melts at 40° and boils at 243°- 245.° Diortho-cyano- 

 benzylacetoacetic ester is a colorless crystalline substance which melts 

 at 1 20.° 



