Acetic Acid → Ethyl 4-acetoxyacetoacetate

HRID 2413986Notes

Reaction equation

HRID 2413986 reaction equation
[C:1]([OH:4])(=[O:3])[CH3:2].C(N(CC)CC)C.Cl[CH2:13][C:14](=[O:21])[CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17]>C(C(C)=O)C(C)C>[C:1]([O:4][CH2:13][C:14](=[O:21])[CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 8471TriethylamineHCID 69484Ethyl 4-chloroacetoacetate

Product 1

HCID 11480907Ethyl 4-acetoxyacetoacetate

Reagents, catalysts & solvents 1

HCID 7909Methyl Isobutyl KetoneSolvent2×

Conditions

Temperature
5 °C

Procedure

A solution of 1.204 l (21.0 moles) of glacial acetic acid and 2.786 l (20.0 moles) of triethylamine in 8.75 l of methyl isobutyl ketone is heated under reflux, and a solution of 1.498 l (11.2 moles) of ethyl 4-chloro-3-oxobutyrate in 1.75 l of methyl isobutyl ketone is added at the boiling point in the course of 20 minutes. When the addition has ended, the mixture is heated under reflux for a further 30 minutes and cooled to about 5° C. and the salts which have precipitated out are filtered off. The residue on the filter is washed with 4.5 l of methyl isobutyl ketone. The combined filtrates are concentrated in vacuo, and first 2 l of drinking water and then 4 l of a 9% strength sodium bicarbonate solution are added to the residue. The suspension is extracted three times with 4 l of ethyl acetate each time and the combined extracts are dried over 2 kg of sodium sulphate, filtered and concentrated in a rotary evaporator at a bath temperature of 40° C.

Workup

  1. temperatureunder reflux
  2. additionWhen the addition
  3. temperaturethe mixture is heated
  4. temperatureunder reflux for a further 30 minutes
  5. customthe salts which have precipitated out
  6. filtrationare filtered off
  7. washThe residue on the filter is washed with 4.5 l of methyl isobutyl ketone
  8. concentrationThe combined filtrates are concentrated in vacuo, and first 2 l of drinking water
  9. addition4 l of a 9% strength sodium bicarbonate solution are added to the residue
  10. extractionThe suspension is extracted three times with 4 l of ethyl acetate each time
  11. dry with materialthe combined extracts are dried over 2 kg of sodium sulphate
  12. filtrationfiltered
  13. concentrationconcentrated in a rotary evaporator at a bath temperature of 40° C.

Sources & evidence

ORD record
ord-131995786ec7429a9da3853e6929984f
Source dataset
uspto-grants-1988_01
Patent number
US04720572

Reaction notes

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