Allyl bromide → HCID 59452984, compound

HRID 419352Notes

Reaction equation

HRID 419352 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4](I)[CH:3]=1.[C:12]1([Mg]Cl)[CH:17]=CC=C[CH:13]=1.C([Cu])#N.C(Br)C=C>C1COCC1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([CH2:17][CH:12]=[CH2:13])[CH:3]=1

Participants

6

Reactant 4

HCID 7841Allyl bromideHCID 193619484-Fluoro-2-iodo-1-nitrobenzeneHCID 178418546HCID 178418546, compoundHCID 178478979HCID 178478979, compound

Product 1

HCID 59452984HCID 59452984, compoundYield 42%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To 4-fluoro-2-iodo-1-nitrobenzene (40.0 g, 150 mmol) in THF (200 mL) at −40° C. was added phenylmagnesium chloride (80.0 mL, 2M in THF, 161 mmol) dropwise. The reaction was stirred for 30 min followed by dropwise addition of CuCN.2LiCl (26.0 g, 150 mmol) in THF. The mixture was stirred an additional 30 min at which time allyl bromide (20.0 g, 161 mmol) was added. The reaction was stirred at −40° C. for 2 h followed by rt overnight. The reaction was quenched with saturated ammonium chloride and extracted with EtOAc. The organic layer was washed with brine, dried (MgSO4) and concentrated. Purification by flash chromatography provided the title compound of step B (11.0 g, 60.7 mmol, 42%). 1H NMR (400 MHz, CDCl3) δ ppm 3.70 (d, J=6.4 Hz, 2H), 5.08-5.71 (m, 2H), 6.87-6.02 (m, 1H), 7.01-7.11 (m, 2H), 7.95-8.05 (m, 1H).

Workup

  1. additionwas added
  2. stirringThe reaction was stirred at −40° C. for 2 h
  3. waitfollowed by rt overnight
  4. customThe reaction was quenched with saturated ammonium chloride
  5. extractionextracted with EtOAc
  6. washThe organic layer was washed with brine
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. customPurification by flash chromatography

Sources & evidence

ORD record
ord-ba674dbad0a6445ca01fdd551ac43752
Source dataset
uspto-grants-2012_01
Patent number
US08093239B2

Reaction notes

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