Benzophenone imine → 3-Bromo-2-chloro-5-fluoroaniline

HRID 629505Notes

Reaction equation

[Br:1][C:2]1[C:3]([Cl:23])=[C:4]([CH:19]=[C:20]([F:22])[CH:21]=1)[N:5]=C(C1C=CC=CC=1)C1C=CC=CC=1.BrC1C=C(F)C=C(Br)C=1Cl.C(=N)(C1C=CC=CC=1)C1C=CC=CC=1.CC(C)([O-])C.[Na+].C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[Br:1][C:2]1[C:3]([Cl:23])=[C:4]([CH:19]=[C:20]([F:22])[CH:21]=1)[NH2:5]

Participants

Conditions

Temperature: 80 °C

Procedure

3-bromo-2-chloro-N-(diphenylmethylene)-5-fluoroaniline. A mixture of 2,6-dibromo-4-fluoro-1-chlorobenzene (865 mg, 3 mmol), benzophenone imine (0.61 ml, 3.6 mmol), Pd2(dba)3 (137 mg, 0.15 mmol), sodium t-butoxide (432 mg, 4.5 mmol), (S)-BINAP (280 mg, 0.45 mmol), and toluene (30 ml) was heated at 80° C. for 16 h. The mixture was extracted with ethyl acetate and the combined organic phase washed with brine. The organic phase was dried over sodium sulfate and concentrated. The crude product was purified by silica gel flash chromatography (40:1 to 20:1 hexanes/ethyl acetate eluant) to provide the title compound as a powder. MS m/z 388.9 (M+1).

Workup

extractionThe mixture was extracted with ethyl acetate
washthe combined organic phase washed with brine
dry with materialThe organic phase was dried over sodium sulfate
concentrationconcentrated
customThe crude product was purified by silica gel flash chromatography (40:1 to 20:1 hexanes/ethyl acetate eluant)

Sources & evidence

ORD record: ord-91605dd75b9649d8b27053750d651815
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09314464B2

Reaction notes

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