Water → 1-Chloro-4-methoxy-5-nitro-2-vinylbenzene

HRID 1019763Notes

Reaction equation

HRID 1019763 reaction equation
Br[C:2]1[CH:7]=[C:6](F)[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[Cl:12].C(Cl)Cl.C(N([CH2:21][CH3:22])CC)C.O.[CH2:24]([OH:27])CC>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:12][C:3]1[CH:4]=[C:5]([N+:9]([O-:11])=[O:10])[C:6]([O:27][CH3:24])=[CH:7][C:2]=1[CH:21]=[CH2:22]

Participants

7

Reactant 5

HCID 962WaterHCID 10311-PropanolHCID 6344DichloromethaneHCID 8471TriethylamineHCID 104001051-Bromo-2-chloro-5-fluoro-4-nitrobenzene

Product 1

HCID 674659471-Chloro-4-methoxy-5-nitro-2-vinylbenzeneYield 75%

Reagents, catalysts & solvents 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Procedure

A mixture of 1-bromo-2-chloro-5-fluoro-4-nitrobenzene (13.0 g, 49.24 mmol), PdCl2(dppf).DCM (0.804 g, 0.98 mmol), potassium ethenyl(trifluoro)borate (7.88 g, 59.09 mmol) and triethylamine (6.87 mL, 49.24 mmol) in n-propanol (130 mL) was heated to reflux for 4 hours. The mixture was allowed to cool to room temperature and poured into water (500 mL). The mixture was extracted with DCM (2×300 mL) then the combined organic extracts were dried (Na2SO4) and the solvent removed under reduced pressure. The residue was purified by column chromatography on neutral silica gel using 1-2% ethyl acetate in hexane to give the title compound (7.8 g, 75%) as a white solid.

Workup

  1. temperatureto reflux for 4 hours
  2. extractionThe mixture was extracted with DCM (2×300 mL)
  3. dry with materialthe combined organic extracts were dried (Na2SO4)
  4. customthe solvent removed under reduced pressure
  5. customThe residue was purified by column chromatography on neutral silica gel using 1-2% ethyl acetate in hexane

Sources & evidence

ORD record
ord-0bc8fa9a29274ad99cf421727c93e236
Source dataset
uspto-grants-2014_05
Patent number
US08716287B2

Reaction notes

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