Methanol → HCID 21470369, compound

HRID 273934Notes

Reaction equation

HRID 273934 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:12][CH:11]=1.[Mg].BrC(Br)C.[C:27](Cl)(=[O:31])[C:28](Cl)=[O:29].[CH3:33][OH:34].[Cl-].[NH4+]>C1COCC1>[C:13]1([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:14]=[CH:15][C:10]([O:9][CH2:8][C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[C:27](=[O:31])[C:28]([O:34][CH3:33])=[O:29])=[CH:11][CH:12]=1

Participants

8

Reactant 6

HCID 887MethanolHCID 112011,1-DibromoethaneHCID 25517Ammonium ChlorideHCID 65578Oxalyl chlorideHCID 5462224MagnesiumHCID 15239354HCID 15239354, compound

Product 1

HCID 21470369HCID 21470369, compoundYield 68.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
65 °C

Procedure

In a stream of argon gas, 1-bromo-2-(biphenyl-4-yloxymethyl)benzene (16.96 g, 0.05 mol) in dry THF (70 ml) was dropwise added to a mixture of magnesium (2.43 g, 0.1 mol) and dibromoethane (0.1 ml) in dry THF (10 ml) at 50° to 60° C. over 20 minutes. The reaction mixture was stirred at 65° C. for 1 hour, diluted with dry THF (20 ml) and cooled below 20° C. The mixture was dropwise added to oxalyl chloride (7.61 g, 0.06 mol) in dry THF (150 ml) below -15° C. over 15 minutes, followed by stirring at -75° C. for 1 hour, and anhydrous methanol (12.82 g, 0.4 mol) was added thereto below -50° C., followed by stirring at room temperature for 1 hour. After completion of the reaction, aqueous ammonium chloride (500 ml) was added to the reaction mixture which was then extracted with ether (400 ml). The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (ethyl acetate/toluene) to give methyl 2-[2-(biphenyl-4-yloxymethyl)phenyl]-2-oxoacetate (11.79 g; yield, 68.1%) as pale yellow crystals.

Workup

  1. temperaturecooled below 20° C
  2. stirringby stirring at -75° C. for 1 hour
  3. custombelow -50° C.
  4. stirringby stirring at room temperature for 1 hour
  5. additionwas added to the reaction mixture which
  6. extractionwas then extracted with ether (400 ml)
  7. dry with materialThe extract was dried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica gel chromatography (ethyl acetate/toluene)

Sources & evidence

ORD record
ord-849e483bccb643d68d65f535c0a4568f
Source dataset
uspto-grants-1995_02
Patent number
US05387714

Reaction notes

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