Cesium carbonate → 4-Chloro-1-ethenyl-2-nitrobenzene

HRID 1508519Notes

Reaction equation

HRID 1508519 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[CH:12]([B-](F)(F)F)=[CH2:13].[K+].C(=O)([O-])[O-].[Cs+].[Cs+]>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].C1COCC1>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([CH:12]=[CH2:13])=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 27949042-Bromo-5-chloronitrobenzeneHCID 23679353Potassium vinyltrifluoroborate

Product 1

HCID 151503814-Chloro-1-ethenyl-2-nitrobenzene

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

Bromo-4-chloro-2-nitrobenzene (3 g, 12.69 mmol), potassium vinyltrifluoroborate (2.039 g, 15.23 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.857 g, 2.54 mmol), cesium carbonate (8.27 g, 25.4 mmol) and THF (50 mL) were heated in an 80° C. oil bath overnight. Volatiles were removed under reduced pressure. The pot residue was worked up with brine, extracted with ethyl acetate, dried over Na2SO4, filtered and evaporated to afford a dark mixture. The resulting crude mixture was purified by flash chromatography (SiO2, Biotage 65i cartridge). The column was eluted by an EtOAc/hexane mixture (0% to 10%). Related fractions were pooled and evaporated to afford a yellow solid as the titled compound. 1H-NMR (CDCl3, 600 MHz) δ 7.94 (d, J=2.4 Hz, 1H), 7.60-7.54 (m, 2H), 7.12 (dd, J=17.4, 10.8 Hz, 1H), 5.75 (d, J=16.8 Hz, 1H), 5.52 (d, J=10.8 Hz).

Workup

  1. customVolatiles were removed under reduced pressure
  2. extractionextracted with ethyl acetate
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. customevaporated
  6. customto afford a dark mixture
  7. customThe resulting crude mixture was purified by flash chromatography (SiO2, Biotage 65i cartridge)
  8. washThe column was eluted by an EtOAc/hexane mixture (0% to 10%)
  9. customevaporated

Sources & evidence

ORD record
ord-266fc479fba541a0b08c3fc354bdb520
Source dataset
uspto-grants-2015_12
Patent number
US09221834B2

Reaction notes

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