Homoallyl bromide → HCID 15817164, compound

HRID 1376429Notes

Reaction equation

HRID 1376429 reaction equation
[Mg].Br[CH2:3][CH2:4][CH:5]=[CH2:6].[NH2:7][C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][C:9]=1[C:15](=[O:20])[C:16]([F:19])([F:18])[F:17]>C1COCC1.CCOC(C)=O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>[NH2:7][C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][C:9]=1[C:15]([OH:20])([CH2:6][CH2:5][CH:4]=[CH2:3])[C:16]([F:19])([F:17])[F:18]

Participants

7

Reactant 3

HCID 21241Homoallyl bromideHCID 5462224MagnesiumHCID 109878821-(2-Amino-5-chlorophenyl)-2,2,2-trifluoroethanone

Product 1

HCID 15817164HCID 15817164, compoundYield 76.8%

Reagents, catalysts & solvents 3

HCID 311Citric AcidSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a 300 mL oven dried 3 necked, round bottomed flask with a stirring bar, argon inlet, addition funnel and a reflux condenser was added magnesium (turnings, 3.03 g, 125 mmol) and dry THF (75 mL). To this well stirred mixture was added 4-bromo-1-butene (12.0 mL, 118.21 mmol) at such a rate as to maintain a gentle reflux. When the addition was complete, the mixture was aged 30 min then cooled to 0° C. in an ice bath. To this well stirred solution was added a solution of 1-(2-amino-5-chlorophenyl)-2,2,2-trifluoroethanone (5.00 g, 22.36 mmol) in THF (35 mL), dropwise over 30 min. The cooling bath was allowed to expire and the mixture was stirred 20 h at ambient temperature. The reaction was diluted with EtOAc and 10% aqueous citric acid. This mixture was stirred for 4 h. The layers were separated and the organic phase was washed with aqueous NaHCO3 and brine. Drying (MgSO4), filtration, removal of the solvent in vacuo, and chromatography on 300 g of silica gel using 15% EtOAc in hexane as eluantas eluant gave 4.80 g of (+/-) 2-(2-amino-5-chlorophenyl)-1,1,1-trifluoro-5-hexen-2-ol as a yellow solid.

Workup

  1. customTo a 300 mL oven dried 3 necked
  2. additionround bottomed flask with a stirring bar, argon inlet, addition funnel and a reflux condenser
  3. temperatureto maintain a gentle reflux
  4. additionWhen the addition
  5. waitdropwise over 30 min
  6. stirringthe mixture was stirred 20 h at ambient temperature
  7. stirringThis mixture was stirred for 4 h
  8. customThe layers were separated
  9. washthe organic phase was washed with aqueous NaHCO3 and brine
  10. customDrying
  11. filtration(MgSO4), filtration, removal of the solvent in vacuo, and chromatography on 300 g of silica gel using 15% EtOAc in hexane as eluantas eluant

Sources & evidence

ORD record
ord-348fa6ce24b14e87b7156f98e9ba2360
Source dataset
uspto-grants-1997_09
Patent number
US05663169

Reaction notes

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