Sodium Formate → 7-Fluoroquinoline-6-carbaldehyde

HRID 456050Notes

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

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 e.q.) 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 rt and concentrated under reduced pressure. The residue was partitioned between water (100 mL) and ethyl acetate (150 mL). The organic layer was separated, washed with brine (100 mL), dried over Na2SO4 and concentrated under reduced pressure. The reside was purified by column choromatography, eluting with petroleum:ethyl acetate=10:1˜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

temperaturecooled to rt
concentrationconcentrated under reduced pressure
customThe residue was partitioned between water (100 mL) and ethyl acetate (150 mL)
customThe organic layer was separated
washwashed with brine (100 mL)
dry with materialdried over Na2SO4
concentrationconcentrated under reduced pressure
customThe reside was purified by column choromatography
washeluting with petroleum

Sources & evidence

ORD record: ord-899d9ddf6da3423f866f6eb2b983a8b3
Source dataset: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08497368B2

Reaction notes

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