ACETO ACETIC ESTER III 



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 suifuric acid and which is probably nitroacetoacetic 

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

 pyrazolone [ i 13:4:5]. Sodacetoacetic ester and iodacetoacetic ester 

 give diacetosuccinic ester. lodacetoacetic ester and metallic silver give 



CH 3 COCCO 2 R 

 diacetofumaric ester, COCCO R' Cupracetoacetic ester boiled in 



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

 phosphorus acts on cupracetoacetic ester to form acetoacetic ester and 

 tri-ethyl phosphite, P (OC 2 H 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 Orthocyanobenzylchlorid on Sodacetoacetic Ester. 



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

 cyanobenzylacetoacetic ester, CH 3 COC (CNC 6 H 4 CH 2 ) 2 CO 2 C 2 H 5 , 

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

 cyanohydro-cinnamic ester, (CNC 6 H 4 CH 2 ) CH 2 CO 2 C 2 H 5 . The latter 

 is a colorless, crystalline substance melting at 98-99 which is decom- 

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



CO 

 dioxid, alcohol and ammonia. a-Hydrindone. Ce H 4 < OT T > CH 2 , 



crystallizes and melts at 40 and boils at 243-245? Diortho-cyano- 

 benzylacetoacetic ester is a colorless crystalline substance which melts 

 at 1 20. 



