2-(Trifluoromethyl)benzeneboronic acid → HCID 50994275, compound

HRID 1518112Notes

Reaction equation

HRID 1518112 reaction equation
Br[C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[C:5]([NH2:12])=[C:4]([N+:13]([O-:15])=[O:14])[CH:3]=1.[F:16][C:17]([F:28])([F:27])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1B(O)O>CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[N+:13]([C:4]1[C:5]([NH2:12])=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=[C:2]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=2[C:17]([F:28])([F:27])[F:16])[CH:3]=1)([O-:15])=[O:14]

Participants

5

Reactant 2

HCID 27343872-(Trifluoromethyl)benzeneboronic acidHCID 108506724-Bromo-2-nitro-6-(trifluoromethyl)aniline

Product 1

HCID 50994275HCID 50994275, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

4-Bromo-2-nitro-6-trifluoromethyl-phenylamine (10.0 g, 35.2 mmol, as prepared in the previous step), 2-trifluoromethylphenylboronic acid (8.70 g, 45.8 mmol), and (dppf)PdCl2 DCM (1.44 g, 1.76 mmol) were placed in a 500 mL round-bottom flask equipped with a magnetic stir bar and reflux condenser. The flask was evacuated and backflushed with Ar. DME (150 mL) and 2M aq Na2 CO3 (50.0 mL, 100 mmol) were added via cannula. The mixture was stirred at 90° C. for 18 h. The mixture was cooled to RT, diluted with EtOAc (100 mL), then washed with water (100 mL) and brine (100 mL). The combined aqueous layers were extracted twice with EtOAc (50 mL). The combined organic extracts were dried over MgSO4, filtered, and the solvent was removed under reduced pressure. The residue was purified on an 80-g pre-packed SiO2 column eluting with EtOAc/hexanes, 0:1 to 1:4, v/v over 30 min, yielding 11.3 g (92%) of the title compound. 1H-NMR (400 MHz, CDCl3) δ: 8.35 (d, J=2.0 Hz, 1H), 7.78 (d, J=7.8 Hz, 1H), 7.74 (s, 1H), 7.61 (t, J=7.2 Hz, 1H), 7.53 (t, J=7.6 Hz, 1H), 7.33 (d, J=7.6 Hz, 1H), 6.75 (br. s., 2H).

Workup

  1. customwere placed in a 500 mL round-bottom flask
  2. customequipped with a magnetic stir bar
  3. temperaturereflux condenser
  4. customThe flask was evacuated
  5. temperatureThe mixture was cooled to RT
  6. washwashed with water (100 mL) and brine (100 mL)
  7. extractionThe combined aqueous layers were extracted twice with EtOAc (50 mL)
  8. dry with materialThe combined organic extracts were dried over MgSO4
  9. filtrationfiltered
  10. customthe solvent was removed under reduced pressure
  11. customThe residue was purified on an 80-g pre-packed SiO2 column
  12. washeluting with EtOAc/hexanes, 0:1 to 1:4, v/v over 30 min

Sources & evidence

ORD record
ord-eb4893b00947478d9f81a82c9f65d07b
Source dataset
uspto-grants-2012_07
Patent number
US08232409B2

Reaction notes

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