Bromobenzene → HCID 59480060, compound

HRID 2068448Notes

Reaction equation

HRID 2068448 reaction equation
C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.Br[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[F:21][C:22]1[CH:23]=[C:24]([CH:26]=[CH:27][C:28]=1[F:29])[NH2:25].CC(C)([O-])C.[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)C.C1(C)C=CC=CC=1>[F:21][C:22]1[CH:23]=[C:24]([NH:25][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:26]=[CH:27][C:28]=1[F:29]

Participants

8

Reactant 4

HCID 7961BromobenzeneHCID 774693,4-DifluoroanilineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxide

Product 1

HCID 59480060HCID 59480060, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

In a 300-mL three-neck flask were placed 200 mL of toluene, 0.21 g (0.96 mmol) of palladium acetate, and an ellipsoidal stirring chip. The two outer necks were closed with septum caps and the center neck was provided with a reflux coiled condenser. To the top of the condenser was attached a three-way stopcock, to which is attached a balloon filled with nitrogen gas. The atmosphere in the flask was replaced three times by nitrogen gas supplied from the balloon with the help of a vacuum pump. Into the flask was injected 3.8 g (18.9 mmol) of tris-t-butylphosphine by means of a syringe, followed by stirring for five to ten minutes at room temperature. The flask was further charged with 10 g (63.7 mmol) of 4-bromobenzene, 4.11 g (31.8 mmol) of 3,4-difluoroaniline, and 6.1 g (63.7 mmol) of sodium t-butoxide. With the flask placed on an oil bath, the solution therein was gradually heated to 120° C. with stirring. After 20 hours, the flask was dismounted from the oil bath so as to terminate reaction, and the solution was allowed to cool to room temperature in an atmosphere of nitrogen. The reaction solution was transferred to a separatory funnel and was given 70 mL of diethyl ether. It was washed several times with 100 mL of saturated aqueous solution of sodium chloride. The organic layer was separated and dried with anhydrous magnesium sulfate. With the anhydrous magnesium sulfate filtered out, the organic layer was freed of solvent by means of an evaporator. Thus there was obtained a crude product, which was subsequently purified by means of a silica gel column (hexane:chloroform=2:1) (Yields: 92%).

Workup

  1. customIn a 300-mL three-neck flask were placed
  2. customThe two outer necks were closed with septum caps
  3. customthe center neck was provided with a reflux
  4. additionfilled with nitrogen gas
  5. customWith the flask placed on an oil bath
  6. temperaturethe solution therein was gradually heated to 120° C.
  7. stirringwith stirring
  8. customto terminate
  9. customreaction
  10. temperatureto cool to room temperature in an atmosphere of nitrogen
  11. customThe reaction solution was transferred to a separatory funnel
  12. washIt was washed several times with 100 mL of saturated aqueous solution of sodium chloride
  13. customThe organic layer was separated
  14. dry with materialdried with anhydrous magnesium sulfate
  15. filtrationWith the anhydrous magnesium sulfate filtered out
  16. customthe organic layer was freed of solvent by means of an evaporator

Sources & evidence

ORD record
ord-727b57a7edf442ef8e002082a9246381
Source dataset
uspto-grants-2012_10
Patent number
US08298444B2

Reaction notes

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