Diethyl Ether → (3-Bromo-phenyl)-cyclopropyl-methyl-amine

HRID 1869955Notes

Reaction equation

HRID 1869955 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N:8]([CH3:11])[CH:9]=O)[CH:5]=[CH:6][CH:7]=1.[CH2:12]([Mg]Br)[CH3:13].CCOCC.C(OCC)(=O)C>O1CCCC1.CCCCCC>[Br:1][C:2]1[CH:3]=[C:4]([N:8]([CH:9]2[CH2:13][CH2:12]2)[CH3:11])[CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 8857Ethyl AcetateHCID 12030886N-(3-Bromo-phenyl)-N-methyl-formamide2×HCID 178418443HCID 178418443, compound

Product 1

HCID 21107154(3-Bromo-phenyl)-cyclopropyl-methyl-amineYield 15%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A stirred, cooled (0° C.) solution of N-(3-bromo-phenyl)-N-methyl-formamide (Intermediate 112, 2.6 g, 9.7 mmol) and titanium tetra-iso-propoxide (3.9 mL, 10.67 mmol) in tetrahydrofuran (40 mL) was treated with a 3M solution of ethyl magnesium bromide in ether (8.08 mL, 24.25 mmol) under argon and the resulting reaction mixture was allowed to warm to ambient temperature gradually and refluxed at 55° C. overnight. It was then cooled in an ice-bath, quenched with saturated aqueous ammonium chloride solution, filtered over celite and the aqueous phase was extracted with diethyl ether. The organic phase was dried over anhydrous magnesium sulfate, filtered and evaporated in vacuo to afford an oil. Flash column chromatography over silica gel (230-400 mesh) using 1.5% ethyl acetate in hexane as the eluent afforded the title compound (0.321 g, 15%).

Workup

  1. customthe resulting reaction mixture
  2. temperaturerefluxed at 55° C. overnight
  3. temperatureIt was then cooled in an ice-bath
  4. customquenched with saturated aqueous ammonium chloride solution
  5. filtrationfiltered over celite
  6. extractionthe aqueous phase was extracted with diethyl ether
  7. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customevaporated in vacuo
  10. customto afford an oil

Sources & evidence

ORD record
ord-2110cc51edd64c989a6295443218b353
Source dataset
uspto-grants-2009_12
Patent number
US07638648B2

Reaction notes

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