1,2-Dimethoxyethane → 3,6-DI-Tert-butyl-2,7-diphenyl-9H-fluorene

HRID 1050669Notes

Reaction equation

HRID 1050669 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.CO[CH2:26][CH2:27]OC.[C:30]1(OB(O)O)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.C(=O)([O-])[O-].[Na+].[Na+]>C(O)C>[C:30]1([C:2]2[C:14]([C:15]([CH3:17])([CH3:18])[CH3:16])=[CH:13][C:12]3[C:11]4[C:6](=[CH:7][C:8]([C:27]5[CH:26]=[CH:4][CH:3]=[CH:2][CH:14]=5)=[C:9]([C:19]([CH3:20])([CH3:22])[CH3:21])[CH:10]=4)[CH2:5][C:4]=3[CH:3]=2)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

6

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 78412Phenyl dihydrogen orthoborateHCID 135475422,7-Dibromo-3,6-DI-tert-butyl-9H-fluorene

Product 1

HCID 219826953,6-DI-Tert-butyl-2,7-diphenyl-9H-fluorene

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Under a nitrogen stream, a 300-mL three-necked flask was charged with 8.15 g (18.7 mmol) of 2,7-dibromo-3,6-di-t-butyl-fluorene and 1.08 g (0.93 mmol) of Pd(PPh3), and further charged with 120 ml of 1,2-dimethoxyethane. The mixture was stirred at room temperature for 20 minutes. To this solution, 20 ml of an ethanol solution in which 5.01 g (41.1 mmol) of phenylboric acid was dissolved was added, and the mixture was stirred at room temperature for 20 minutes. Thereafter, 37.4 ml (74.8 mmol) of a 2.0 mol/L aqueous solution of sodium carbonate was added. Subsequently, the mixture was heated to reflux for 18 hours, left to be naturally cooled, and quenched with dilute hydrochloric acid in an ice bath. Thereafter, ether was added to extract the soluble fraction, and the organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water, and two times with saturated brine, and then dried over magnesium sulfate. Then, magnesium sulfate was separated by filtration, and the filtrate distillation under reduced pressure using a rotary evaporator to remove the solvent. The resulting solids were purified by column chromatography to obtain a target product (yield 4.36 g (54%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. additionwas added
  2. stirringthe mixture was stirred at room temperature for 20 minutes
  3. temperatureSubsequently, the mixture was heated
  4. temperatureto reflux for 18 hours
  5. waitleft
  6. temperatureto be naturally cooled
  7. customquenched with dilute hydrochloric acid in an ice bath
  8. additionThereafter, ether was added
  9. extractionto extract the soluble fraction
  10. washthe organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water, and two times with saturated brine
  11. dry with materialdried over magnesium sulfate
  12. customThen, magnesium sulfate was separated by filtration
  13. distillationthe filtrate distillation under reduced pressure
  14. customa rotary evaporator
  15. customto remove the solvent
  16. customThe resulting solids were purified by column chromatography
  17. customto obtain a target product (yield 4.36 g (54%))

Sources & evidence

ORD record
ord-a6f5b90cc41845688cbe10bf192e1b74
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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