Dimethylformamide → Methyl 2'-fluoro-5'-(methyloxy)-2-nitro-1,1'-biphenyl-4-carboxylate

HRID 404342Notes

Reaction equation

Cl[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13].CN(C=O)C.[F:20][C:21]1[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][C:22]=1B(O)O.C(=O)([O-])[O-].[K+].[K+]>[Cl-].[Na+].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:20][C:21]1[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][C:22]=1[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13]

Participants

Conditions

Temperature: 90 °C

Procedure

To a stirred solution of methyl 4-chloro-3-nitrobenzoate (10.00 g, 46 mmol, commercially available from TCI) in DMF (15.00 mL, 194 mmol) at 23° C. was added 2-fluoro-5-methoxyphenylboronic acid (12 g, 70 mmol) (commercially available from Sigma-Aldrich, St. Louis, Mo., USA), potassium carbonate (19 g, 139 mmol), and then tetrakis(triphenylphosphine)palladium (2.1 g, 1.9 mmol). The mixture was heated at 90° C. for 18 hours and then cooled to room temperature. The reaction was diluted with brine and extracted three times with EtOAc. The organic layers were combined, dried over anhydrous MgSO4, and filtered. The organic solvent was removed under reduced pressure and the residue was purified on silica gel (0-40% EtOAc in hexanes) to yield T12.3 as a colorless oil (14.00 g, 99% yield).

Workup

temperaturecooled to room temperature
extractionextracted three times with EtOAc
dry with materialdried over anhydrous MgSO4
filtrationfiltered
customThe organic solvent was removed under reduced pressure
customthe residue was purified on silica gel (0-40% EtOAc in hexanes)

Sources & evidence

ORD record: ord-0e3180df4ea746a5a105839c707d01c2
Source dataset: uspto-grants-2014_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08748462B2

Reaction notes

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