2-Fluoroaniline → 2-Fluorodiphenylamine

HRID 1776162Notes

Reaction equation

I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[F:14][C:15]1[CH:21]=[CH:20][CH:19]=[CH:18][C:16]=1[NH2:17]>C1(C)C=CC=CC=1.O.CCOCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:14][C:15]1[CH:21]=[CH:20][CH:19]=[CH:18][C:16]=1[NH:17][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 115 °C

Procedure

A reaction vessel was charged with iodobenzene (1.42 g, 7 mmol), palladium(II) acetate (0.079 g, 0.35 mmol), 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.217 g, 0.35 mmol), cesium carbonate (6.8 g, 21 mmol), 2-fluoroaniline (0.777 g, 7 mmol) in anhydrous toluene (18 mL). Under a nitrogen atmosphere, the mixture was heated at 115° C. for 24 hours. The cooled mixture was diluted with water and ether. The organic layer was isolated, washed with saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated to a residue. The crude product was purified by silica gel column chromatography (0-30% ethyl acetate in hexanes) to give the desired product as a clear oil (1.1 g, 81%). 1H NMR (CDCl3, 300 MHz) δ 7.36-7.29 (m, 3H), 7.20-7.14 (m, 3H), 7.09-7.00 (m, 2H), 6.88-6.85 (m, 1H), 5.82 (br s, 1H). ESI m/z: 188.2 (M+H).

Workup

customThe organic layer was isolated
washwashed with saturated aqueous sodium chloride
dry with materialdried (anhydrous sodium sulfate)
filtrationfiltered
concentrationconcentrated to a residue
customThe crude product was purified by silica gel column chromatography (0-30% ethyl acetate in hexanes)

Sources & evidence

ORD record: ord-93fead06df444600b875789b013ce9f9
Source dataset: uspto-grants-2016_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09265772B2

Reaction notes

Loading…