Sodium Carbonate → 3-Fluoro-5-nitrobiphenyl

HRID 530379Notes

Reaction equation

HRID 530379 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4](I)[CH:3]=1.[C:12]1(B(O)O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)([O-])[O-].[Na+].[Na+]>C(OCC)(=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].O.C(COC)OC>[F:1][C:2]1[CH:3]=[C:4]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 80271Tri-o-tolylphosphineHCID 2590861-Fluoro-3-iodo-5-nitrobenzene

Product 1

HCID 900418983-Fluoro-5-nitrobiphenyl

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A suspension of 1-fluoro-3-iodo-5-nitrobenzene (11.0 g, 41.3 mmol), phenyl boronic acid (5.54 g, 45.4 mmol), tri-o-tolylphosphine (1.26 g, 4.13 mmol), Pd(OAc)2 (0.463 g, 2.07 mmol), and sodium carbonate (6.57 g, 62.0 mmol) in 4:1 dimethoxyethane:water (80 mL) was heated to 100° C. in a sealed tube for 6 hours. Upon cooling to ambient temperature, the reaction mixture was diluted with ethyl acetate (500 mL) and filtered through CELITE. The organic layer was washed with brine (500 mL) and concentrated in vacuo. The residue was purified by silica gel column chromatography (ethyl acetate/hexanes) provided 3-fluoro-5-nitrobiphenyl as an off-white solid. 1H NMR (400 MHz, CDCl3) δ 8.31 (s, 1H), 7.93 (dt, J=8.1 Hz, 2.1 Hz, 1H), 7.72-7.60 (m, 3H), 7.51 (ddd, J=10.9, 9.9, 5.6 Hz, 3H).

Workup

  1. filtrationfiltered through CELITE
  2. washThe organic layer was washed with brine (500 mL)
  3. concentrationconcentrated in vacuo
  4. customThe residue was purified by silica gel column chromatography (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-8f0d7d39695f4ff7a5d028341efe98b2
Source dataset
uspto-grants-2016_05
Patent number
US09353066B2

Reaction notes

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