Acetic Acid → Methyl 4-(acetyloxy)-3-oxobutanoate

HRID 329801

Reaction equation

HRID 329801 reaction equation
[C:1]([O-:4])(=[O:3])[CH3:2].[K+].C(O)(=O)C.Cl[CH2:11][C:12](=[O:18])[CH2:13][C:14]([O:16][CH3:17])=[O:15]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(#N)C>[C:1]([O:4][CH2:11][C:12](=[O:18])[CH2:13][C:14]([O:16][CH3:17])=[O:15])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 36240Methyl 4-chloroacetoacetateHCID 517044Potassium Acetate

Product 1

HCID 13130412Methyl 4-(acetyloxy)-3-oxobutanoateYield 61%

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 6342AcetonitrileSolvent2×

Procedure

108 g (1.1 mol) of potassium acetate and 11.4 g (0.05 mol) of benzyltriethylammonium chloride are suspended in 900 ml of acetonitrile, treated with 50 ml of acetic acid and heated to reflux temperature. Within 31/2 hours there are added dropwise thereto 150.5 g (1 mol) of methyl 4-chloroacetoacetate in 100 ml of acetonitrile and the mixture is subsequently held at reflux temperature for 4 hours. The reaction mixture is washed 3 times with 200 ml of 5% NaH2PO4 solution each time and the aqueous phases are back-extracted with 200 ml of CH2Cl2. The combined organic phases are dried over magnesium sulphate and concentrated on a rotary evaporator. The crude product distils at 76°-85° C./0.6 mbar and gives 106.17 g (61%) of methyl 4-acetoxyacetoacetate.

Workup

  1. temperatureheated
  2. temperatureto reflux temperature
  3. additionWithin 31/2 hours there are added dropwise
  4. temperatureat reflux temperature for 4 hours
  5. washThe reaction mixture is washed 3 times with 200 ml of 5% NaH2PO4 solution each time
  6. extractionthe aqueous phases are back-extracted with 200 ml of CH2Cl2
  7. dry with materialThe combined organic phases are dried over magnesium sulphate
  8. concentrationconcentrated on a rotary evaporator
  9. customThe crude product distils at 76°-85° C./0.6 mbar

Sources & evidence

ORD record
ord-8c3bf2c931e84e6699fd0c91310bafde
Source dataset
uspto-grants-1990_01
Patent number
US04892966

Linked notes

Loading…