Toluene → HCID 11290100, compound

HRID 380708Notes

Reaction equation

HRID 380708 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][CH:4]=1)#[CH:2].Br[C:11]1[CH:12]=[C:13]([CH:23]=[CH:24][CH:25]=1)[C:14]([C:16]1[CH:21]=[CH:20][C:19]([F:22])=[CH:18][CH:17]=1)=[O:15].C1(C)C=CC=CC=1>C(N(CC)CC)C>[F:9][C:6]1[CH:7]=[CH:8][C:3]([C:1]#[C:2][C:24]2[CH:25]=[CH:11][CH:12]=[C:13]([C:14](=[O:15])[C:16]3[CH:17]=[CH:18][C:19]([F:22])=[CH:20][CH:21]=3)[CH:23]=2)=[CH:4][CH:5]=1

Participants

5

Reactant 3

HCID 1140TolueneHCID 5226271-Ethynyl-4-fluorobenzeneHCID 36501933-Bromo-4'-fluorobenzophenone2×

Product 1

HCID 11290100HCID 11290100, compound

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent2×

Conditions

Temperature
80 °C

Procedure

Thus a reaction mixture is formed by dissolving appropriate amounts of 1-ethynyl-4-fluorobenzene, 3-bromo-4′-fluorobenzophenone, and tetrakis(triphenylphosphine)palladium[0] in a de-aerated aprotic solvent, for example, triethylamine. Alternatively, toluene can be used as a first solvent and triethylamine added as a cosolvent in a stoichiometric equivalent to 3-bromo-4′-fluorobenzophenone. The reaction mixture is heated to 80° C. with stirring under an inert atmosphere, e.g. argon, for approximately three hours. The reaction mixture is then allowed to cool to ambient while stirring is continued for approximately 16 hours. A white precipitate of triethylamine hydrobromide is removed by filtration and the aprotic solvents employed are removed by evaporation. The resulting solids are dissolved in a solvent, e.g. dichloromethane, or preferably toluene due to its relatively higher environmental friendliness, and then washed with water, an aqueous 2% HCl solution, brine, and then dried. After solvent evaporation, a good yield of white crystalline 4-fluoro-3′-(4-fluorobenzoyl)tolane, melting at approximately 127-128° C. is obtained. Purification by recrystallization from acetone results in a material with a melting point of 130-131° C. Alternatively, recrystallization from toluene provide a crystalline material in the form of rhombic fine needles with a melting point of 135-136° C.

Workup

  1. customThus a reaction mixture is formed
  2. temperatureto cool to ambient
  3. stirringwhile stirring
  4. waitis continued for approximately 16 hours
  5. customA white precipitate of triethylamine hydrobromide is removed by filtration
  6. customthe aprotic solvents employed are removed by evaporation
  7. dissolutionThe resulting solids are dissolved in a solvent, e.g. dichloromethane, or preferably toluene due to its relatively higher environmental friendliness
  8. washwashed with water
  9. dry with materialan aqueous 2% HCl solution, brine, and then dried
  10. customAfter solvent evaporation

Sources & evidence

ORD record
ord-3d2ed1ef62ff4e73a979731ce73143f4
Source dataset
uspto-grants-2001_10
Patent number
US06303733B1

Reaction notes

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