ChemicalBook Product Catalog Chemical Reagents Organic reagents Esters Ethyl ester compound Ethyl 4-chloroacetoacetate

Ethyl 4-chloroacetoacetate

Product NameEthyl 4-chloroacetoacetate
CAS638-07-3
MFC6H9ClO3
MW164.59
EINECS211-317-0
MOL File638-07-3.mol

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.)
Flash point	206 °F
storage temp.	2-8°C
solubility	47.0g/l
form	Liquid
pka	9.56±0.46(Predicted)
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)

Safety Information

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

MSDS

Provider	Language
Ethyl 4-chloro-3-oxobutanoate	English
SigmaAldrich	English
ACROS	English
ALFA	English

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

141-97-9

638-07-3

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).