1-Bromo-4-fluorobenzene → HCID 86702136, compound

HRID 1776192Notes

Reaction equation

HRID 1776192 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][CH:3]=1.[Cl:9][C:10]1[CH:16]=[C:15]([F:17])[CH:14]=[CH:13][C:11]=1[NH2:12].CC(C)([O-])C.[Na+]>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].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C1(C)C=CC=CC=1>[Cl:9][C:10]1[CH:16]=[C:15]([F:17])[CH:14]=[CH:13][C:11]=1[NH:12][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 99931-Bromo-4-fluorobenzeneHCID 75013Benzenamine, 2-chloro-4-fluoro-HCID 23676156Sodium t-butoxide

Product 1

HCID 86702136HCID 86702136, compoundYield 68.5%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A round bottom flask was charged with 1-bromo-4-fluorobenzene (6.011 g, 34.4 mmol), 2-chloro-4-fluoroaniline (5.000 g, 34.3 mmol), Xantphos (0.795 g, 1.4 mmol), anhydrous toluene (200 mL), and sodium tert-butoxide (4.952 g, 51.5 mmol). The mixture was degassed and filled with nitrogen, and then tris(dibenzylideneacetone)dipalladium(0) (0.944 g, 1.0 mmol) was added and the reaction was stirred under nitrogen at 100° C. for 16 hrs. After cooling to room temperature, the mixture was filtered through Celite and the filter cake washed with methylene chloride. The filtrate was concentrated and the residue purified by silica gel chromatography (0-20% ethyl acetate/hexanes) to afford a yellowish oil (5.63 g, 68%). 1H NMR (300 MHz, CDCl3) δ 7.14 (dd, 1H, J=8.4, 3.0 Hz), 7.12-6.98 (m, 5H), 6.88 (td, 1H, J=8.7, 3.0 Hz), 5.80 (br s, 1H).

Workup

  1. customThe mixture was degassed
  2. additionfilled with nitrogen
  3. temperatureAfter cooling to room temperature
  4. filtrationthe mixture was filtered through Celite
  5. washthe filter cake washed with methylene chloride
  6. concentrationThe filtrate was concentrated
  7. customthe residue purified by silica gel chromatography (0-20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-06e1a9ea411b491da9568dc82ded6430
Source dataset
uspto-grants-2016_02
Patent number
US09265772B2

Reaction notes

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