4-Chlorophenol → Ethyl 2-(4-chlorophenoxy)acetoacetate

HRID 703057Notes

Reaction equation

HRID 703057 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1.Cl[CH:12]([C:18]([CH3:20])=[O:19])[C:13]([O:15][CH2:16][CH3:17])=[O:14]>C1(C)C=CC=CC=1>[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([O:10][CH:12]([C:18]([CH3:20])=[O:19])[C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 46844-ChlorophenolHCID 11858Ethyl 2-chloroacetoacetateHCID 24758Sodium hydride

Product 1

HCID 15678688Ethyl 2-(4-chlorophenoxy)acetoacetateYield 37%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
80 °C

Procedure

A 60% dispersion of sodium hydride in mineral oil (40 g, 1 mol) was washed with dry petroleum ether and suspended in dry toluene (700 ml). The suspension was stirred under argon and carefully treated with a solution of 4-chlorophenol (128.6 g, 1 mol) in dry toluene (300 ml) added dropwise. The resulting suspension was stirred for 1 hour, warmed to 80° C. and treated with ethyl 2-chloroacetoacetate (165 g, 1 mol) added dropwise to maintain the internal temperature between 80°-85° C. The resulting solution was stirred at 80° C. for 4 hours, cooled and carefully treated with ice. The organic phase was washed with water (3×200 ml), 10% sodium hydroxide (2×75 ml), 75 ml), water (20 ml) and brine (100 ml), dried with magnesium sulfate, filtered and concentrated. The resulting oil was distilled in vacuo [bp 126°-132° C. (0.1 mm)]to give 95 g (37%) of ethyl 2-(4-chlorophenoxy)-acetoacetate.

Workup

  1. additionadded dropwise
  2. stirringThe resulting suspension was stirred for 1 hour
  3. additionadded dropwise
  4. temperatureto maintain the internal temperature between 80°-85° C
  5. stirringThe resulting solution was stirred at 80° C. for 4 hours
  6. temperaturecooled
  7. additioncarefully treated with ice
  8. washThe organic phase was washed with water (3×200 ml), 10% sodium hydroxide (2×75 ml), 75 ml), water (20 ml) and brine (100 ml)
  9. dry with materialdried with magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. distillationThe resulting oil was distilled in vacuo [bp 126°-132° C. (0.1 mm)]to

Sources & evidence

ORD record
ord-5efb3387e7dc4eaaa04bf7ea747beba8
Source dataset
uspto-grants-1991_01
Patent number
US04981849

Reaction notes

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