Ethanol → Ethyl Acetate

HRID 325998Notes

Reaction equation

HRID 325998 reaction equation
[Na+].[Cl-].[C]=O.[CH3:5][CH2:6][O-:7].[Na+].[CH2:9]([O:11][C:12](=[O:15])[CH2:13][Cl:14])[CH3:10].[CH2:16]([OH:18])C>C1(C)C=CC=CC=1>[CH2:6]([O:7][C:16](=[O:18])[CH2:13][C:12]([O:11][CH2:9][CH3:10])=[O:15])[CH3:5].[CH2:9]([O:11][C:12](=[O:15])[CH2:13][Cl:14])[CH3:10].[CH2:9]([O:11][C:12](=[O:15])[CH3:13])[CH3:10]

Participants

9

Reactant 5

HCID 702Ethanol2×HCID 5234Sodium ChlorideHCID 7751Ethyl chloroacetateHCID 2723922Sodium ethoxide3×HCID 178418416HCID 178418416, compound

Product 3

HCID 7751Ethyl chloroacetateHCID 7761Diethyl MalonateHCID 8857Ethyl AcetateYield 1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
55 °C

Procedure

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.

Workup

  1. customIn a pressure vessel of a capacity of 7.5 liters, equipped with a pH
  2. additionthe liquid and gas phases being thoroughly mixed by means of a circulating pump
  3. temperatureto maintain a pH of approximately 7.0
  4. waitOver a period of 6 hours
  5. temperatureThen the vessel is cooled
  6. customthe vessel is purged with nitrogen
  7. customThe reaction solution is separated from the sodium chloride on a suction
  8. filtrationfilter
  9. distillationdistilled

Sources & evidence

ORD record
ord-173c42b622d94c21963a01bd10960989
Source dataset
uspto-grants-1984_04
Patent number
US04443624

Reaction notes

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