Sodium Carbonate → 1-Fluoro-2-nitro-3-(prop-1-en-2-yl)benzene

HRID 1475609Notes

Reaction equation

HRID 1475609 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1[N+:9]([O-:11])=[O:10].O1CCOCC1.C(=O)([O-])[O-].[Na+].[Na+].[CH3:24][C:25]1(C)[C:29](C)(C)OB(C(C)=C)O1>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.O>[F:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:25]([CH3:29])=[CH2:24])[C:3]=1[N+:9]([O-:11])=[O:10]

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 27831521-Bromo-3-fluoro-2-nitrobenzeneHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane

Product 1

HCID 866914681-Fluoro-2-nitro-3-(prop-1-en-2-yl)benzeneYield 75.3%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 1-bromo-3-fluoro-2-nitrobenzene (0.953 g, 4.33 mmol) in a 100 mL round-bottomed flask equipped with a magnetic stir bar and nitrogen inlet were added dioxane (17.3 mL), sodium carbonate (0.551 g, 5.20 mmol), water (4.33 mL), and 4,4,5,5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane (0.977 mL, 5.20 mmol). To this mixture was added bis(triphenyl-phosphine)palladium(II)chloride (0.243 g, 0.347 mmol). The flask was evacuated and purged with nitrogen (3×) and then heated to 80° C. and stirred overnight. The reaction was cooled to room temperature, filtered through Celite®, and the pad was washed with ethyl acetate. The phases were separated and the organic phase was concentrated. Purification by flash column chromatography provided the title compound (0.590 g, 3.26 mmol, 75% yield) as a light yellow oil: 1H NMR (400 MHz, CDCl3) δ 7.48-7.36 (m, 1H), 7.21-7.06 (m, 2H), 5.23 (p, J=1.5 Hz, 1H), 5.05 (q, J=1.1 Hz, 1H), 2.09 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 153.56 (d, JCF=257.5 Hz), 139.62, 139.60, 138.83, 131.48 (d, JCF=8.6 Hz), 124.47 (d, JCF=3.6 Hz), 117.60, 115.51 (d, JCF=19.1 Hz), 23.18.

Workup

  1. customequipped with a magnetic stir bar and nitrogen inlet
  2. customThe flask was evacuated
  3. custompurged with nitrogen (3×)
  4. temperatureThe reaction was cooled to room temperature
  5. filtrationfiltered through Celite®
  6. washthe pad was washed with ethyl acetate
  7. customThe phases were separated
  8. concentrationthe organic phase was concentrated
  9. customPurification by flash column chromatography

Sources & evidence

ORD record
ord-978fdec2d04f492ab839ed8782ef4aca
Source dataset
uspto-grants-2015_04
Patent number
US09018388B2

Reaction notes

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