Hydrochloric Acid → HCID 86623194, compound

HRID 1050663Notes

Reaction equation

HRID 1050663 reaction equation
Br[C:2]1[C:14]([C:15]([CH3:18])([CH3:17])[CH3:16])=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8](Br)=[C:9]([C:19]([CH3:22])([CH3:21])[CH3:20])[CH:10]=3)[CH2:5][C:4]=2[CH:3]=1.P([C:33]([CH3:36])([CH3:35])[CH3:34])(C(C)(C)C)C(C)(C)C.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C:45]1([CH3:54])[CH:50]=[CH:49][CH:48]=[CH:47][C:46]=1B(O)O.Cl.O1C[CH2:59][CH2:58][CH2:57]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].C(OCC)C>[C:33]1([CH3:34])[CH:35]=[CH:59][C:58]([C:13]2[C:14]([C:15]([CH3:17])([CH3:18])[CH3:16])=[CH:2][C:3]3[C:7]4[C:6](=[CH:11][C:10]([C:48]5[CH:49]=[CH:50][C:45]([CH3:54])=[CH:46][CH:47]=5)=[C:9]([C:19]([CH3:21])([CH3:20])[CH3:22])[CH:8]=4)[CH2:5][C:4]=3[CH:12]=2)=[CH:57][CH:36]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 8028Tetrahydrofuran2×HCID 62657Potassium Phosphate, TribasicHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 27332672-Methylphenyl boronic acidHCID 135475422,7-Dibromo-3,6-DI-tert-butyl-9H-fluorene

Product 1

HCID 86623194HCID 86623194, compoundYield 14%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 3283Diethyl EtherSolvent

Procedure

Under a nitrogen atmosphere, 50 mL of dehydrated tetrahydrofuran was added to 3.50 g (8.02 mmol) of 2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis Example 1-1(i), 0.186 g (0.20 mmol) of Pd2(dba)3, 0.115 g (0.57 mmol) of P(tBu)3, and 6.81 g (32.1 mmol) of tripotassium phosphate, and the mixture was stirred at room temperature for 20 minutes. To the solution, a solution of 2.73 g (20.0 mmol) prepared by dissolving o-tolylboronic acid in 15 mL of dehydrated tetrahydrofuran was added. Subsequently, the mixture was heated to reflux for 72 hours, left to be naturally cooled, and then 1N hydrochloric acid was added in an ice bath to terminate the reaction. Thereafter, diethylether was added to perform liquid-liquid phase separation. The aqueous layer was extracted twice with diethylether and the resultant was combined with the organic layer obtained previously. Then, the resultant liquid washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water, and once with saturated brine, and dried over magnesium sulfate. Subsequently, the solvent was distilled off, and the resultant was subjected to separation by silica gel chromatography to obtain a target product as a white powder (yield 0.532 g (14%)). The target product was identified by 1H-NMR.

Workup

  1. customTo the solution, a solution of 2.73 g (20.0 mmol) prepared
  2. additionwas added
  3. temperatureSubsequently, the mixture was heated
  4. temperatureto reflux for 72 hours
  5. waitleft
  6. temperatureto be naturally cooled
  7. customto terminate
  8. customthe reaction
  9. customliquid-liquid phase separation
  10. extractionThe aqueous layer was extracted twice with diethylether
  11. customobtained previously
  12. washThen, the resultant liquid washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  13. dry with materialonce with saturated brine, and dried over magnesium sulfate
  14. distillationSubsequently, the solvent was distilled off
  15. customthe resultant was subjected to separation by silica gel chromatography

Sources & evidence

ORD record
ord-d2891d6834704235b1b4d6f769ac9d28
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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