Chloroacetone → Methyl 4-acetoxy-2-acetonylacetoacetate

HRID 329802Notes

Reaction equation

HRID 329802 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].[C:7]([O:10][CH2:11][C:12](=[O:18])[CH2:13][C:14]([O:16][CH3:17])=[O:15])(=[O:9])[CH3:8].Cl[CH2:20][C:21](=[O:23])[CH3:22]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(#N)C>[C:7]([O:10][CH2:11][C:12](=[O:18])[CH:13]([CH2:20][C:21]([CH3:22])=[O:23])[C:14]([O:16][CH3:17])=[O:15])(=[O:9])[CH3:8]

Participants

6

Reactant 3

HCID 6571ChloroacetoneHCID 10340Sodium CarbonateHCID 13130412Methyl 4-(acetyloxy)-3-oxobutanoate

Product 1

HCID 19871662Methyl 4-acetoxy-2-acetonylacetoacetateYield 92%

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 6342AcetonitrileSolvent

Procedure

63.6 g (0.6 mol) of sodium carbonate and 2.3 g (0.01 mol) of benzyltriethylammonium chloride are suspended in 250 ml of acetonitrile. While stirring there are added thereto 87.0 g (0.5 mol) of methyl 4-acetoxyacetoacetate and there are added dropwise thereto within 5 minutes 69.4 g (0.75 mol) of chloroacetone. The mixture is stirred at 20°-25° C. for a further 46 hours. The reaction mixture is poured on to 1 liter of 10% NaH2PO4 solution/ice (pH value=5) and extracted 3 times with 300 ml of ethyl acetate each time. The combined organic phases are dried over magnesium sulphate and concentrated completely on a rotary evaporator to give 105.9 g (92%) of methyl 4-acetoxy-2-acetonylacetoacetate, content 76.9%; b.p. 119°-121° C./0.06 mbar.

Workup

  1. additionare added
  2. stirringThe mixture is stirred at 20°-25° C. for a further 46 hours
  3. extractionextracted 3 times with 300 ml of ethyl acetate each time
  4. dry with materialThe combined organic phases are dried over magnesium sulphate
  5. concentrationconcentrated completely on a rotary evaporator

Sources & evidence

ORD record
ord-4e716ffc8bb34572ba310a512e5c975f
Source dataset
uspto-grants-1990_01
Patent number
US04892966

Reaction notes

Loading…