Dichloromethane → 2'-Chloro-5-nitro-3-trifluoromethyl-biphenyl-4-ylamine

HRID 1518140Notes

Reaction equation

HRID 1518140 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.[Cl:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1B(O)O.C(Cl)Cl>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]>[Cl:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:2]1[CH:3]=[C:4]([N+:13]([O-:15])=[O:14])[C:5]([NH2:12])=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 27343222-Chlorophenylboronic acidHCID 108506724-Bromo-2-nitro-6-(trifluoromethyl)aniline

Product 1

HCID 509942772'-Chloro-5-nitro-3-trifluoromethyl-biphenyl-4-ylamineYield 94%

Reagents, catalysts & solvents 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Conditions

Temperature
90 °C

Procedure

4-Bromo-2-nitro-6-trifluoromethyl-phenylamine (1.01 g, 3.55 mmol), 2-chlorophenylboronic acid (1.5 eq., 833 mg, 5.33 mmol), and (dppf)PdCl2.DCM (0.05 eq., 145 mg, 0.178 mmol) were placed in a 40 mL vial equipped with a magnetic stir bar. The vial was evacuated and backflushed with Ar, and DME (15 mL) and 2M aq Na2 CO3 (5 mL) were added via syringe. The vial was capped tightly and placed in a heating block where the reaction was stirred at 90° C. for 18 h. The mixture was cooled to rt, diluted with EtOAc, and washed with water. The aqueous layers were combined and extracted with EtOAc. The combined organic extracts were dried over anhydrous MgSO4, filtered, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a 24-g SiO2 pre-packed column eluting with EtOAc/hexanes, 0 to 1:4, v/v over 20 min, yielding 1.05 g (94%) of the desired compound. 1H-NMR (400 MHz, CDCl3) δ: 8.47 (d, J=2.0 Hz, 1H), 7.89 (d, J=2.0 Hz, 1H), 7.47-7.53 (m, 1H), 7.30-7.37 (m, 3H), 6.76 (br. s., 2H).

Workup

  1. customvial equipped with a magnetic stir bar
  2. customThe vial was evacuated
  3. additionCO3 (5 mL) were added via syringe
  4. customThe vial was capped tightly
  5. temperatureThe mixture was cooled to rt
  6. additiondiluted with EtOAc
  7. washwashed with water
  8. extractionextracted with EtOAc
  9. dry with materialThe combined organic extracts were dried over anhydrous MgSO4
  10. filtrationfiltered
  11. customthe solvent was removed under reduced pressure
  12. customThe crude product was purified by column chromatography
  13. washeluting with EtOAc/hexanes, 0 to 1:4, v/v over 20 min

Sources & evidence

ORD record
ord-c3b35139f107404983e20475083311be
Source dataset
uspto-grants-2012_07
Patent number
US08232409B2

Reaction notes

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