Potassium Carbonate → HCID 58233563, compound

HRID 239209Notes

Reaction equation

HRID 239209 reaction equation
[C:1]1([C:7]2([C:20]3[CH:21]=[C:22](B(O)O)[CH:23]=[CH:24][CH:25]=3)[C:19]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[C:13]3[C:8]2=[CH:9][CH:10]=[CH:11][CH:12]=3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Br:29][C:30]1[CH:35]=[CH:34][CH:33]=[C:32](I)[CH:31]=1.C(=O)([O-])[O-].[K+].[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.O.C1(C)C=CC=CC=1.C(O)C>[Br:29][C:30]1[CH:31]=[C:32]([C:22]2[CH:21]=[C:20]([C:7]3([C:1]4[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=4)[C:8]4[CH:9]=[CH:10][CH:11]=[CH:12][C:13]=4[C:14]4[C:19]3=[CH:18][CH:17]=[CH:16][CH:15]=4)[CH:25]=[CH:24][CH:23]=2)[CH:33]=[CH:34][CH:35]=1

Participants

9

Reactant 3

HCID 11430Potassium CarbonateHCID 11561Benzene, 1-bromo-3-iodo-HCID 67105798HCID 67105798, compound

Product 1

HCID 58233563HCID 58233563, compoundYield 80%

Reagents, catalysts & solvents 5

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent2×

Procedure

In a 50 mL three-neck flask were put 1.2 g (3.2 mmol) of [3-(9-phenyl-9H-fluoren-9-yl)phenyl]boronic acid and 54.7 mg (0.2 mmol) of tris(2-methylphenyl)phosphine. The air in the flask was replaced with nitrogen. To this mixture were added 12.0 mL of toluene, 4.0 mL of ethanol, 0.5 mL (3.5 mmol) of 1-bromo-3-iodobenzene, and 3.2 mL of an aqueous solution of potassium carbonate (2 mol/L). The temperature of this mixture was set to 60° C., and then 13.9 mg (0.1 mmol) of palladium(II) acetate was added to the mixture. The temperature of this mixture was set to 80° C., followed by reflux for 3.0 hours. After the reflux, toluene and water were added to this mixture, the organic layer and the aqueous layer were separated, and the aqueous layer was extracted three times with toluene. This toluene layer and the organic layer were combined, washed with saturated brine, and dried with magnesium sulfate. The obtained mixture was gravity filtered so that magnesium sulfate was removed, and the obtained filtrate was concentrated to give a solid. Recrystallization of the solid from a mixed solvent of toluene and methanol gave 1.2 g of a white solid in 80% yield, which was the substance to be produced. The synthesis scheme of this Step 2 is shown in (E18-2) given below.

Workup

  1. customIn a 50 mL three-neck flask were put
  2. customwas set to 60° C.
  3. customwas set to 80° C.
  4. temperatureby reflux for 3.0 hours
  5. customthe organic layer and the aqueous layer were separated
  6. extractionthe aqueous layer was extracted three times with toluene
  7. washwashed with saturated brine
  8. dry with materialdried with magnesium sulfate
  9. filtrationfiltered so that magnesium sulfate
  10. customwas removed
  11. concentrationthe obtained filtrate was concentrated
  12. customto give a solid
  13. customRecrystallization of the solid from a mixed solvent of toluene and methanol

Sources & evidence

ORD record
ord-9cf11621bbea41ceb97aa4ac854b685f
Source dataset
uspto-grants-2014_02
Patent number
US08642190B2

Reaction notes

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