1-(Bromomethyl)-3-phenoxybenzene → Ethyl 1-(p-chlorophenyl)-beta-oxo-alpha-(m-phenoxybenzyl)cyclopropanepropionate

HRID 1741432Notes

Reaction equation

HRID 1741432 reaction equation
[Na].[Cl:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2([C:12](=[O:19])[CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:11][CH2:10]2)=[CH:5][CH:4]=1.[C:20]1([O:26][C:27]2[CH:28]=[C:29]([CH2:33]Br)[CH:30]=[CH:31][CH:32]=2)[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>C(O)C>[Cl:2][C:3]1[CH:4]=[CH:5][C:6]([C:9]2([C:12](=[O:19])[CH:13]([CH2:33][C:29]3[CH:30]=[CH:31][CH:32]=[C:27]([O:26][C:20]4[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=4)[CH:28]=3)[C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:11][CH2:10]2)=[CH:7][CH:8]=1

Participants

5

Reactant 3

HCID 945441-(Bromomethyl)-3-phenoxybenzeneHCID 5360545Sodium2×HCID 21835800Ethyl 1-(p-chlorophenyl)-beta-oxocyclopropanepropionate

Product 1

HCID 11070385Ethyl 1-(p-chlorophenyl)-beta-oxo-alpha-(m-phenoxybenzyl)cyclopropanepropionateYield 92%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Conditions

Temperature
70 °C

Procedure

A mixture of sodium (0.31 g, 13.5 mmol) in ethanol (90 mL) is stirred at room temperature until the sodium dissolves. The resultant solution is heated to 70° C., treated dropwise with a solution of ethyl 1-(p-chlorophenyl)-β-oxocyclopropanepropionate (3.4 g, 12.8 mmol) in ethanol, stirred at 70° C. for one hour, treated dropwise with a solution of α-bromo-m-tolyl phenyl ether (4.0 g, 15.2 mmol) in ethanol, stirred at reflux overnight, stirred at room temperature for two days, and concentrated in vacuo to obtain a residue. A solution of the residue in ethyl acetate is washed sequentially with water, 10% sodium hydrogen carbonate solution and brine, dried over anhydrous sodium sulfate, and concentrated in vacuo to obtain an oil. Chromatography of the oil using silica gel and a 19:1 hexanes/ethyl acetate solution gives the title product as a colorless oil (5.24 g, 92%) which is identified by NMR spectral analysis.

Workup

  1. dissolutiondissolves
  2. stirringstirred
  3. temperatureat reflux overnight
  4. stirringstirred at room temperature for two days
  5. concentrationconcentrated in vacuo
  6. customto obtain a residue
  7. washA solution of the residue in ethyl acetate is washed sequentially with water, 10% sodium hydrogen carbonate solution and brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated in vacuo
  10. customto obtain an oil

Sources & evidence

ORD record
ord-386b673c226c4aec94b59ee7b4b8fc44
Source dataset
uspto-grants-1999_10
Patent number
US05973190

Reaction notes

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