4-Bromo-2-nitroaniline → 2'-Fluoro-3-nitro-[1,1'-biphenyl]-4-amine

HRID 1518142Notes

Reaction equation

HRID 1518142 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.[F:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1B(O)O.C([O-])(O)=O.[Na+]>O1CCOCC1.O.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>[F:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1

Participants

7

Reactant 3

HCID 701324-Bromo-2-nitroanilineHCID 516892Sodium BicarbonateHCID 27343542-Fluorophenylboronic acid

Product 1

HCID 224778582'-Fluoro-3-nitro-[1,1'-biphenyl]-4-amineYield 78%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 4-bromo-2-nitro-phenylamine (2.17 g, 10.0 mmol) in dioxane (40 mL) was treated with 2-fluorophenylboronic acid (1.40 g, 10.0 mmol) and NaHCO3 (40.0 mL, 80.0 mmol, 2M aqueous). The mixture was degassed via sonication and flushed with Ar. Pd(PPh3)4 (116 mg, 0.100 mmol) was added, and the mixture was heated to 80° C. for 12 h. The mixture was diluted with water (40 mL) and extracted twice with EtOAc (40 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo. The residue was purified on silica (EtOAc/hexanes, 0:1 to 1:1, v/v) to obtain 1.80 g (78%) of the title compound. 1H-NMR (400 MHz, CDCl3) δ: 8.36 (d, J=1.8 Hz, 1H), 7.64 (dt, J=8.6, 2.0 Hz, 1H), 7.45 (td, J=7.8, 1.8 Hz, 1H), 7.30-7.38 (m, 1H), 7.13-7.27 (m, 2H), 6.91 (d, J=8.6 Hz, 1H), 6.18 (br. s., 2H).

Workup

  1. customThe mixture was degassed via sonication
  2. customflushed with Ar
  3. extractionextracted twice with EtOAc (40 mL)
  4. dry with materialThe combined organic layers were dried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified on silica (EtOAc/hexanes, 0:1 to 1:1

Sources & evidence

ORD record
ord-8e13399615f143f28a896fea6299fbf6
Source dataset
uspto-grants-2012_07
Patent number
US08232409B2

Reaction notes

Loading…