Dimethyl Carbonate → Methyl 3-(3-bromo-4-fluorophenyl)-3-oxopropanoate

HRID 2186214Notes

Reaction equation

HRID 2186214 reaction equation
[H-].[Na+].[C:3](=[O:8])([O:6][CH3:7])OC.[Br:9][C:10]1[CH:11]=[C:12]([C:17](=[O:19])[CH3:18])[CH:13]=[CH:14][C:15]=1[F:16]>O1CCCC1.C(OCC)(=O)C>[Br:9][C:10]1[CH:11]=[C:12]([C:17](=[O:19])[CH2:18][C:3]([O:6][CH3:7])=[O:8])[CH:13]=[CH:14][C:15]=1[F:16]

Participants

6

Reactant 3

HCID 12021Dimethyl CarbonateHCID 24758Sodium hydrideHCID 705081-(3-Bromo-4-fluorophenyl)ethan-1-one

Product 1

HCID 18177311Methyl 3-(3-bromo-4-fluorophenyl)-3-oxopropanoateYield 26.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

To a suspension of sodium hydride (1.1 g of 60% suspension in mineral oil, hexane-washed, 27.6 mmol) in 50 mL of tetrahydrofuran was added dimethyl carbonate (2.3 mL, 27.6 mmol) and 3′-bromo-4′-fluoroacetophenone (3.0 g, 13.8 mmol). The resulting suspension was stirred at 65° C. for 1 h and then was cooled to room temperature. The reaction mixture was diluted with ethyl acetate and washed with water and brine, dried (MgSO4) and concentrated in vacuo. The residue was purified by flash chromatography (elution with 3:1 hexane/ethyl acetate) to afford 1.0 g (26%) of the title compound. 1H NMR (CDCl3) (data for keto tautomer) δ8.15 (dd, 1H), 7.87 (m, 1H), 7.2 (m, 1H), 3.95 (s, 2H), 3.73 (s, 3H).

Workup

  1. temperaturewas cooled to room temperature
  2. washwashed with water and brine
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by flash chromatography (elution with 3:1 hexane/ethyl acetate)

Sources & evidence

ORD record
ord-fe7484d33cd04e389070b2ecd02d9b7b
Source dataset
uspto-grants-2002_06
Patent number
US06403620B1

Reaction notes

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