Ethyl bromoacetate → HCID 54297555, compound

HRID 1596706Notes

Reaction equation

HRID 1596706 reaction equation
O[C:2]1[CH:3]=[C:4]([C:9](=O)[CH3:10])[CH:5]=[C:6](O)[CH:7]=1.BrCC(OCC)=O.C([O-])([O-])=O.[K+].[K+].[CH2:25]([O:27][C:28](=[O:41])[CH2:29][O:30][C:31]1[CH:36]=[C:35]([OH:37])[CH:34]=[C:33]([C:38](=[O:40])[CH3:39])[CH:32]=1)[CH3:26].C(OC(=O)COC1C=C(OCC(OCC)=O)C=C(C(=O)C)C=1)C.C(OC(=O)COC1C=C(OCC(OC)=O)C=C(C(=O)C)C=1)C.BrC(C1C=CC=CC=1)C>CC(C)=O>[C:38]([C:33]1[CH:34]=[C:35]([O:37][CH:9]([C:4]2[CH:5]=[CH:6][CH:7]=[CH:2][CH:3]=2)[CH3:10])[CH:36]=[C:31]([CH:32]=1)[O:30][CH2:29][C:28]([O:27][CH2:25][CH3:26])=[O:41])(=[O:40])[CH3:39]

Participants

9

Reactant 7

HCID 7748Ethyl bromoacetateHCID 11430Potassium Carbonate2×HCID 11454(1-Bromoethyl)benzeneHCID 1039933',5'-Dihydroxyacetophenone3×HCID 54053002HCID 54053002, compoundHCID 54234792HCID 54234792, compoundHCID 54541323HCID 54541323, compound2×

Product 1

HCID 54297555HCID 54297555, compound

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent2×

Procedure

To a solution of 3′,5′-dihydroxyacetophenone (10.0 g, 66 mmol) and ethyl bromoacetate (11.0 g, 66 mmol) in acetone (300 mL) is added K2CO3 (9.0 g, 66 mmol), and the resulting mixture is refluxed for 3 hours. After cooling, the mixture is filtered, and the filtrate is concentrated in vacuo. The residue is chromatographed (silica, 3:2 hexane/EtOAc) to give a mixture of (3-acetyl-5-hydroxyphenoxy)-acetic acid ethyl ester, 3′,5′-dihydroxyacetophenone and [3-acetyl-5-(ethoxycarbonylmethoxy)-phenoxy]-acetic acid ethyl ester (the dialkylation product), which is carried on to the next step without further purification. To a solution of ethyl (3-acetyl-5-hydroxyphenoxy)-acetate (2.4 g, 10.1 mmol), contaminated with 3′,5′-dihydroxyacetophenone and (3-acetyl-5-methoxycarbonylmethoxyphenoxy) acetic acid ethyl ester, and (1-bromoethyl)benzene (2.24 g, 12.1 mmol) in acetone (100 mL) is added K2CO3 (2.09 g, 15.1 mmol), and the resulting mixture is refluxed for 3 hours. After cooling, the mixture is filtered, and the filtrate is concentrated in vacuo. The residue is chromatographed (silica, 3:1 hexane/EtOAc) to give ethyl [5-acetyl-3-(1-phenylethoxy)-phenoxy]-acetate.

Workup

  1. temperaturethe resulting mixture is refluxed for 3 hours
  2. temperatureAfter cooling
  3. filtrationthe mixture is filtered
  4. concentrationthe filtrate is concentrated in vacuo
  5. customThe residue is chromatographed (silica, 3:2 hexane/EtOAc)
  6. customto give
  7. customis carried on to the next step without further purification
  8. temperaturethe resulting mixture is refluxed for 3 hours
  9. temperatureAfter cooling
  10. filtrationthe mixture is filtered
  11. concentrationthe filtrate is concentrated in vacuo
  12. customThe residue is chromatographed (silica, 3:1 hexane/EtOAc)

Sources & evidence

ORD record
ord-046d598b3d2b44358c964f6a07a20c3b
Source dataset
uspto-grants-2001_09
Patent number
US06291530B1

Reaction notes

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