Sodium Bicarbonate → HCID 86656183, compound

HRID 1192699Notes

Reaction equation

HRID 1192699 reaction equation
[Cl:1][C:2]1[C:3]([C:23]#[N:24])=[C:4]([N+:20]([O-:22])=[O:21])[C:5](OS(C(F)(F)F)(=O)=O)=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[F:25][C:26]1[CH:27]=[C:28](B(O)O)[CH:29]=[CH:30][CH:31]=1.C([O-])(O)=O.[Na+]>C1(C)C=CC=CC=1.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>[Cl:1][C:2]1[CH:11]=[C:6]([C:7]([O:9][CH3:10])=[O:8])[C:5]([C:30]2[CH:29]=[CH:28][CH:27]=[C:26]([F:25])[CH:31]=2)=[C:4]([N+:20]([O-:22])=[O:21])[C:3]=1[C:23]#[N:24]

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 27339863-Fluorophenylboronic acidHCID 86656182HCID 86656182, compound

Product 1

HCID 86656183HCID 86656183, compoundYield 40%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a biphasic solution of methyl 5-chloro-4-cyano-3-nitro-2-{[(trifluoromethyl)sulfonyl]oxy}benzoate (3.60 g, 9.26 mmol) and (3-fluorophenyl)boronic acid (1.42 g, 10.2 mmol) in toluene (80 mL) was added saturated NaHCO3 (80 mL) and then the reaction was bubbled with N2 to degas. Tetrakis(triphenylphosphine)palladium(0) (0.535 g, 0.463 mmol) was added. The resulting mixture was bubbled with N2 for 5 minutes and then heated at 80° C. for 2 hours. After cooling to room temperature, the mixture was diluted with ethyl acetate. The layers were separated and the aq. layer was extracted with ethyl acetate. The combined extracts were washed with brine, dried over Na2SO4, filtered, and concentrated. The resulting residue was purified on silica gel column, eluting with ethyl acetate/hexane, 0-30%, to give the desired product (1.23 g, 40%). LCMS calculated for C15H9ClFN2O4 (M+H)+: m/z=335.0; Found: 335.1. 1H NMR (CDCl3, 400 MHz) δ 8.14 (1H, s), 7.40 (1H, m), 7.20 (1H, m), 6.97 (1H, m), 6.93 (1H, m), 3.66 (3H, s) ppm.

Workup

  1. customthe reaction was bubbled with N2
  2. customto degas
  3. customThe resulting mixture was bubbled with N2 for 5 minutes
  4. temperatureAfter cooling to room temperature
  5. additionthe mixture was diluted with ethyl acetate
  6. customThe layers were separated
  7. extractionthe aq. layer was extracted with ethyl acetate
  8. washThe combined extracts were washed with brine
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe resulting residue was purified on silica gel column
  13. washeluting with ethyl acetate/hexane, 0-30%

Sources & evidence

ORD record
ord-20760cdf62534655b32d84ca43097cf7
Source dataset
uspto-grants-2014_03
Patent number
US08680108B2

Reaction notes

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