Cesium carbonate → 6-Fluoro-3',5'-dimethoxy-4-nitrobiphenyl-3-carbaldehyde

HRID 56463

Reaction equation

Br[C:2]1[C:3]([F:13])=[CH:4][C:5]([N+:10]([O-:12])=[O:11])=[C:6]([CH:9]=1)[CH:7]=[O:8].[CH3:14][O:15][C:16]1[CH:17]=[C:18](B(O)O)[CH:19]=[C:20]([O:22][CH3:23])[CH:21]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.O.C1(P([Pd-](Cl)P(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:13][C:3]1[C:2]([C:18]2[CH:17]=[C:16]([O:15][CH3:14])[CH:21]=[C:20]([O:22][CH3:23])[CH:19]=2)=[CH:9][C:6]([CH:7]=[O:8])=[C:5]([N+:10]([O-:12])=[O:11])[CH:4]=1

Participants

Conditions

Temperature: 90 °C

Procedure

A mixture of 5-bromo-4-fluoro-2-nitrobenzaldehyde (10.0 g, 40.0 mmol), 3,5-dimethoxyphenylboronic acid (7.3 g, 40.0 mmol), bis(triphenylphosphino) palladium(II) chloride (1.4 g, 2.0 mmol) and cesium carbonate (32.6 g, 100.0 mmol) in dioxane/water (550 mL, v/v=10/1) was degassed with nitrogen for three times and heated at 90° C. for 3 hours. The mixture was cooled to room temperature, concentrated, diluted with ethyl acetate (1000 mL), and washed by water (500 mL) and brine (500 mL). The organic layer was dried, concentrated, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate=8/1 to 5/1) to afford the title compound (9 g, 61%) as a yellow solid. MS (ES+) C15H12FNO5 requires: 305, found: 306 [M+H]+.

Workup

customwas degassed with nitrogen for three times
temperatureThe mixture was cooled to room temperature
concentrationconcentrated
additiondiluted with ethyl acetate (1000 mL)
washwashed by water (500 mL) and brine (500 mL)
customThe organic layer was dried
concentrationconcentrated
customthe residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate=8/1 to 5/1)

Sources & evidence

ORD record: ord-da5102f3143b4fe5bc503d2f4daeb2f6
Source dataset: uspto-grants-2016_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09434700B2

Linked notes

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