Aceto acetic acid Alkyl derivatives

Reaction XLIV. (b) Condensation of Alkyl and Aryl Halogen Compounds with the Sodio- and other Metallo-derivatives of Ethyl Aceto-acetate and its Homolognes. (A., 186, 214 201, 143 213, 143.)—Like malonic ester, acetoacetic ester contains two 1 3-carbonyl groups with a methylene group in position 2. It is only to be expected then that it yields with metallic sodium or sodium alcoholate sodio-derivatives from which mono- and di-, alkyl and aryl homologues can be obtained by treatment with a suitable halide, including halogen esters. Acetoacetic acid... 

Aceto Acetic Ester S3mtheses.— These alkyl and acyl derivatives of ethyl aceto acetate, both the mono- and the di- derivatives, react now on hydrolysis in the two ways given above, i.e.y by Xheketonehydro-lysis or the acid hydrolysis and we may thus obtain a large number of ketones and acids as desired. 

Action of Hydrogen and of Ammonia.— Another reaction of aceto acetic ester should be mentioned. When hydrogen (sodium amalgam), ammonia or alkyl primary amines react with aceto acetic ester, crotonic acid (p. 173) CHs—CH = CH—COOH, or derivatives of it are obtained. The fact that crotonic acid contains a double bond seems to indicate the presence of a double bond in aceto acetic ester, and would be evidence for the enol form. 

Fragmentations of heterocycles have played an important role in the preparation of amide derivatives. Moderate to good yields of a-hydroxy-amides were obtained on reaction of a-hydroxy-acid aceto-nides with primary amines.N-Alkyl-2-methyl-2-oxazolinium salts (obtained by mixing alkyl halides and 2-methyl-2-oxazoline in dichloromethane) were found to react with sodium benzeneselenolate to yield -(2-phenylselenoethyl)-t -alkylacetamides, which after oxidation to ] -vinyl analogues with sodium metaperiodate in methanol, gave secondary amides on sequential treatment with mercuric acetate in aqueous tetrahydrofuran and sodium borohydride/3M... 

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