Ethyl Bromide → HCID 18357814, compound

HRID 1857814Notes

Reaction equation

HRID 1857814 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][O:9][CH:10]1[CH2:15][CH2:14][CH2:13][CH2:12][O:11]1.C(Br)C.[Mg].[C:20](Cl)(=[O:24])[C:21](Cl)=[O:22].[CH3:26][NH2:27].CO>O.C1COCC1>[CH3:26][NH:27][C:20](=[O:24])[C:21](=[O:22])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:8][O:9][CH:10]1[CH2:15][CH2:14][CH2:13][CH2:12][O:11]1

Participants

8

Reactant 5

HCID 6332Ethyl BromideHCID 65578Oxalyl chlorideHCID 53150262-[(2-Bromophenyl)methoxy]oxaneHCID 5462224MagnesiumHCID 57454252Monomethylamine methanol

Product 1

HCID 18357814HCID 18357814, compoundYield 42.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
55 °C

Procedure

A mixed solution of 1-bromo-2-(2-tetrahydropyranyloxymethyl)benzene (2.71 g, 0.01 mol) and dry THF (8 ml) was added dropwise at 50 to 60° C. over 20 minutes to a solution prepared by adding dry THF (2 ml) and ethyl bromide (0.1 ml) to magnesium (0.36 g, 0.015 mol) in a stream of nitrogen. After completion of the addition, the mixture was stirred at 50 to 60° C. for 1 hour and cooled to room temperature. After cooling, the mixture was added dropwise to a mixed solution of oxalyl chloride (1.90 g, 0.015 mol) and dry THF (30 ml) at below -50° C. over 15 minutes. Then, the mixture was stirred at -60 to -70° C. for 40 minutes. A 40% methylamine-methanol solution (4.66 g, 0.06 mol) was added to the reaction mixture, and the mixture was stirred at -20 to -10° C. for 30 minutes. After completion of the reaction, water (150 ml) was added, and the mixture was extracted with ether (150 ml). The extract was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (ethyl acetate/n-hexane) to obtain N-methyl-2-oxo-2-[2-(2-tetrahydropyranyloxymethyl)phenyl]acetamide(1.18 g, Yield: 42.5%) as a colorless oil.

Workup

  1. customprepared
  2. additionAfter completion of the addition
  3. temperaturecooled to room temperature
  4. temperatureAfter cooling
  5. stirringThen, the mixture was stirred at -60 to -70° C. for 40 minutes
  6. stirringthe mixture was stirred at -20 to -10° C. for 30 minutes
  7. additionwas added
  8. extractionthe mixture was extracted with ether (150 ml)
  9. washThe extract was washed with saturated brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. concentrationconcentrated under reduced pressure
  12. customThe resulting residue was purified by silica gel chromatography (ethyl acetate/n-hexane)

Sources & evidence

ORD record
ord-13e4ca84baa942a694d9745eac70a48d
Source dataset
uspto-grants-2000_11
Patent number
US06147231

Reaction notes

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