Hydrochloric Acid → HCID 67117368, compound

HRID 1784670Notes

Reaction equation

HRID 1784670 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[O:9][CH3:10].[Mg].BrCCBr.[C:16](OCC)(=[O:22])[C:17]([O:19][CH2:20][CH3:21])=[O:18].Cl>O1CCCC1.C(OCC)C.O>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:16](=[O:22])[C:17]([O:19][CH2:20][CH3:21])=[O:18])=[C:3]([O:9][CH3:10])[CH:4]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 7268Diethyl OxalateHCID 78391,2-DibromoethaneHCID 5462224MagnesiumHCID 70180432-Bromo-5-fluoroanisole

Product 1

HCID 67117368HCID 67117368, compoundYield 59.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

A solution of 2-bromo-5-fluoroanisole (11.8 g, 57.6 mmol) in tetrahydrofuran (60 ml) was dropped into the magnesium (1.40 g, 57.6 mmol) in refluxed tetrahydrofuran (32 ml) containing small amount of 1,2-dibromoethane and refluxed for 15 min. After addition of tetrahydrofuran (50 ml), the solution was cooled to −78° C. and diethyl oxalate (7.41 g; 50.7 mmol) in diethyl ether (50 ml) was dropped into the solution. After stirring at the same temperature for 30 min, the solution was warmed to −10° C. and 1N aqueous hydrogen chloride (50 ml) and water were added. Organic layer was extracted with diethyl ether, washed with brine and dried over magnesium sulfate. After removal of the solvent under reduced pressure, purification of the residue by silica gel column chromatography (eluent: hexane/ethyl acetate=5/2) gave ethyl 2-(4-fluoro-2-methoxyphenyl)-2-oxoacetate (6.80 g, 59%)

Workup

  1. temperaturerefluxed for 15 min
  2. temperaturethe solution was warmed to −10° C.
  3. extractionOrganic layer was extracted with diethyl ether
  4. washwashed with brine
  5. dry with materialdried over magnesium sulfate
  6. customAfter removal of the solvent
  7. customunder reduced pressure, purification of the residue by silica gel column chromatography (eluent: hexane/ethyl acetate=5/2)

Sources & evidence

ORD record
ord-f3214dec4a244d639a6af1e5525a6813
Source dataset
uspto-grants-2009_03
Patent number
US07504411B2

Reaction notes

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