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| | Ethyl 4-chloroacetoacetate Basic information |
| | Ethyl 4-chloroacetoacetate Chemical Properties |
| Melting point | -8 °C | | Boiling point | 115 °C/14 mmHg (lit.) | | density | 1.218 g/mL at 25 °C (lit.) | | vapor pressure | 7hPa at 20℃ | | refractive index | n20/D 1.452(lit.) | | Fp | 206 °F | | storage temp. | 2-8°C | | solubility | 47.0g/l | | pka | 9.56±0.46(Predicted) | | form | Liquid | | color | Clear colorless to pale reddish-yellow | | PH | 2.9 (10g/l, H2O, 20℃) | | explosive limit | 1.8%(V) | | Water Solubility | 47.5 g/L (20 ºC) | | BRN | 1761275 | | InChI | 1S/C6H9ClO3/c1-2-10-6(9)3-5(8)4-7/h2-4H2,1H3 | | InChIKey | OHLRLMWUFVDREV-UHFFFAOYSA-N | | SMILES | CCOC(=O)CC(=O)CCl | | LogP | 0.68 at 25℃ | | CAS DataBase Reference | 638-07-3(CAS DataBase Reference) | | NIST Chemistry Reference | Butanoic acid, 4-chloro-3-oxo-, ethyl ester(638-07-3) | | EPA Substance Registry System | Ethyl 4-chloroacetoacetate (638-07-3) |
| Hazard Codes | T,N,C | | Risk Statements | 25-34-51/53-24/25-36 | | Safety Statements | 26-36-45-61-36/37/39-27 | | RIDADR | UN 2922 8/PG 2 | | WGK Germany | 3 | | RTECS | AK5110000 | | F | 8-10-19-21 | | TSCA | TSCA listed | | HazardClass | 8 | | PackingGroup | II | | HS Code | 29183000 | | Storage Class | 6.1A - Combustible acute toxic Cat. 1 and 2
very toxic hazardous materials | | Hazard Classifications | Acute Tox. 3 Dermal
Acute Tox. 3 Oral
Aquatic Chronic 2
Eye Dam. 1
Skin Corr. 1B |
| | Ethyl 4-chloroacetoacetate Usage And Synthesis |
| Description | Ethyl 4-chloroacetoacetate is a chemical compound, which for the ethyl
esters of acetoacetic acid belongs. It is a starting material in various
syntheses. | | 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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