Sodium Formate → 7-Fluoroquinoline-6-carbaldehyde

HRID 1892286Notes

Reaction equation

HRID 1892286 reaction equation
[CH:1]([O-:3])=O.[Na+].Br[C:6]1[CH:7]=[C:8]2[C:13](=[CH:14][C:15]=1[F:16])[N:12]=[CH:11][CH:10]=[CH:9]2>C(#N)C.CS(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:16][C:15]1[CH:14]=[C:13]2[C:8]([CH:9]=[CH:10][CH:11]=[N:12]2)=[CH:7][C:6]=1[CH:1]=[O:3]

Participants

6

Reactant 2

HCID 2723810Sodium FormateHCID 145483436-Bromo-7-fluoroquinoline

Product 1

HCID 529829097-Fluoroquinoline-6-carbaldehydeYield 10.4%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 679Dimethyl SulfoxideSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
120 °C

Procedure

To a suspension of Pd(PPh3)4 (1.27 g, 1.1 mmol) and sodium formate (13.8 g, 132 mmol, 6 eq.) in acetonitrile (30 mL) was added a solution of 6-bromo-7-fluoro quinoline (5 g, 22 mmol) in DMSO (30 mL). The reaction mixture was heated at 120° C. under a CO atmosphere (1 MPa) for 4 h, cooled to it and concentrated under reduced pressure. The residue was partitioned between water (100 mL) and EtOAc (150 mL). The organic layer was separated, washed with brine (100 mL), dried over Na2SO4 and concentrated under reduced pressure to give a residue, which was purified by column choromatography with gradient petroleum:EtOAc from 10:1 to 3:1 to give the title compound as a white solid (400 mg, 10.4%). 1H-NMR (400 MHz, DMSO-d6) δ ppm 8.95 (s, 1H), 8.46 (m, 1H), 8.20 (m, 1H), 7.75 (d, 1H), 7.53 (m, 1H).

Workup

  1. temperaturecooled to it
  2. concentrationconcentrated under reduced pressure
  3. customThe residue was partitioned between water (100 mL) and EtOAc (150 mL)
  4. customThe organic layer was separated
  5. washwashed with brine (100 mL)
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customto give a residue, which
  9. customwas purified by column choromatography with gradient petroleum

Sources & evidence

ORD record
ord-4b268198a7364fddbf6578dc9673b08b
Source dataset
uspto-grants-2013_08
Patent number
US08507676B2

Reaction notes

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