Ethanol → Ethyl Acetate

Participants

Reaction Conditions

Reaction Steps

In a pressure vessel of a capacity of 7.5 liters, equipped with a pH measuring system, 20 g of Co2 (CO)8, 10 g of NaCl as conducting salt, and 2.5 liters of ethanol denatured with toluene are combined. The apparatus is scavenged three times with carbon monoxide, and then a CO pressure of 7.5 atmospheres gauge is established. While the vessel is heated at 55° C., a solution of 20.5% sodium ethylate in ethanol is pumped in from a reservoir by means of a proportioning pump such that a pH of 7 to 8 is reached, the liquid and gas phases being thoroughly mixed by means of a circulating pump. After the reaction temperature is reached, 490 g (4 moles) Of chloroacetic acid ethyl ester is proportioned into the vessel at a constant CO pressure of 8.0 at. gauge over a period of 15 minutes, and a 20.6% solution of sodium ethylate is added through a second inlet so as to maintain a pH of approximately 7.0. Over a period of 6 hours, 1.12 kg (3.4 moles) of 20.6% sodium ethylate is pumped in. Then the vessel is cooled, the pressure is relieved, and the vessel is purged with nitrogen. The reaction solution is separated from the sodium chloride on a suction filter and distilled. 517 g of malonic acid diethyl ester is obtained (95% yield), plus 2.5 g of acetic acid ethyl ester (approx. 1% yield) and 5 g of high-boiling compounds plus 73 g of chloroacetic acid ethyl ester.

Provenance & Evidence