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| | Ethyl 4-chloroacetoacetate Basic information |
| | Ethyl 4-chloroacetoacetate Chemical Properties |
| | Ethyl 4-chloroacetoacetate Usage And Synthesis |
| Chemical Properties | Ethyl 4-chloroacetoacetate is colorless to pale reddish-yellow clear liquid | | Uses | Ethyl-4-chloracetoacetate (CAAEt) is used as intermediate for organic syntheses, e.g. ethyl 4-chloro-3-arylaminocrotonates, diethyl succinylsuccinate, 2-alkyl-4-hydroxy-6-chloromethylpyrimidines, 4- chloromethylcoumarines. Product Data Sheet | | Uses | Ethyl 4-chloroacetoacetate is used as a precursor in the preparation of phosphorous ylides. It finds application in regular film coating, pharmaceutical coating and formulation. | | Preparation |
Preparative Methods of Ethyl 4-chloroacetoacetate: the industrial production of the esters is made exclusively by chlorination of diketene
followed by reaction of the intermediate acid chloride with the corresponding alcohol.[2]
| | Synthesis | GENERAL PROCEDURE: To an anhydrous THF (2 mL) solution of diisopropylamine (340 μL, 2.4 eq.) in a flame-dried round-bottomed flask under an argon atmosphere at 0 °C, n-butyllithium (1.4 mL, 1.6 M hexane solution, 2.2 eq.) was slowly added and the reaction mixture was stirred at this temperature for 15 min. Maintaining the same temperature, a solution of THF (2 mL) in ethyl acetoacetate (1 mmol) was slowly added dropwise. The reaction mixture was cooled to -78 °C after continued stirring at 0 °C for 1 h. Methyl chlorosulfate (110 μL, 1.2 eq.) was subsequently added. After stirring at -78 °C for 30 min, the reaction was quenched by the addition of saturated aqueous ammonium chloride solution (5 mL). The mixture was extracted with dichloromethane (3 x 5 mL) and the organic phases were combined and dried over anhydrous magnesium sulfate. Evaporation of the solvent gave the target product ethyl 4-chloroacetoacetate. | | Solubility in organics | Ethyl 4-Chloroacetoacetate is is soluble in most organic solvents. The ethyl ester (1a) is 12% enolized in the pure liquid, and highly
enolized (60% in CCl4) in nonpolar solvents.[1] | | storage |
Ethyl 4-chloroacetoacetate is lachrymators of moderate toxicity; uses in a fume
hood.
| | References | 1. Rappoport, Z. The Chemistry of Enols; Wiley: New York, 1990; p 365.
2. Lonza AG; U.S. Patent 4 473 508, 1984 (CA 1985, 102, 5715). |
| | Ethyl 4-chloroacetoacetate Preparation Products And Raw materials |
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