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

HRID 1050676Notes

Reaction equation

HRID 1050676 reaction equation
CO[CH2:3][CH2:4]OC.Br[C:8]1[C:20]([C:21]([CH3:24])([CH3:23])[CH3:22])=[CH:19][C:18]2[C:17]3[C:12](=[CH:13][C:14](Br)=[C:15]([C:25]([CH3:28])([CH3:27])[CH3:26])[CH:16]=3)[CH2:11][C:10]=2[CH:9]=1.[C:30]1(OB(O)O)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>C(O)C>[C:25]([C:15]1[C:14]([C:4]2[CH:3]=[CH:10][CH:9]=[CH:8][CH:20]=2)=[CH:13][C:12]2[CH2:11][C:10]3[C:18]([C:17]=2[CH:16]=1)=[CH:19][C:20]([C:21]([CH3:24])([CH3:22])[CH3:23])=[C:8]([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)[CH:9]=3)([CH3:27])([CH3:26])[CH3:28]

Participants

5

Reactant 3

HCID 80711,2-DimethoxyethaneHCID 78412Phenyl dihydrogen orthoborate2×HCID 135475422,7-Dibromo-3,6-DI-tert-butyl-9H-fluorene

Product 1

HCID 219826953,6-DI-Tert-butyl-2,7-diphenyl-9H-fluoreneYield 54%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Under a nitrogen atmosphere, 120 mL of anhydrous DME was added to 8.15 g (18.7 mmol) of 2,7-dibromo-3,6-di-tert-butylfluorene and 1.08 g (0.93 mmol) of Pd(PPh3), and 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. The flask that had contained the phenylboric acid was washed two times with 4 mL of ethanol, and this was also added to the solution. The mixture was then 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, and left to be naturally cooled, and the reaction was terminated with 1N hydrochloric acid in an ice bath. Thereafter, ether was added to extract the soluble fraction, and the aqueous layer was subjected to extraction with diethyl ether twice. The resultant extract was then combined with the organic layer obtained earlier. The resulting liquid was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water, and once with saturated brine, and then dried over magnesium sulfate. The solvent was distilled off, and the residue was subjected to separation by silica gel chromatography. To the thus obtained whitish yellow powder, a mixture solution of hexane and a small amount of dichloromethane was added, and the mixture was heated to 60° C. to dissolve the powder completely. The resultant solution was left to stand for 1 hour at room temperature and then left to stand for 13 hours at −20° C. Crystals precipitated were washed 3 times with 10 mL of hexane to give a target product as a white powder (yield 4.36 g (54%)).

Workup

  1. additionwas added
  2. washwas washed two times with 4 mL of ethanol
  3. additionthis was also added to the solution
  4. stirringThe mixture was then stirred at room temperature for 20 minutes
  5. additionThereafter, 37.4 mL (74.8 mmol) of a 2.0 mol/L aqueous solution of sodium carbonate was added
  6. temperatureSubsequently, the mixture was heated
  7. temperatureto reflux for 18 hours
  8. waitleft
  9. temperatureto be naturally cooled
  10. customthe reaction was terminated with 1N hydrochloric acid in an ice bath
  11. additionThereafter, ether was added
  12. extractionto extract the soluble fraction
  13. extractionthe aqueous layer was subjected to extraction with diethyl ether twice
  14. extractionThe resultant extract
  15. customobtained earlier
  16. washThe resulting liquid was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  17. dry with materialonce with saturated brine, and then dried over magnesium sulfate
  18. distillationThe solvent was distilled off
  19. customthe residue was subjected to separation by silica gel chromatography
  20. additionTo the thus obtained whitish yellow powder, a mixture solution of hexane and a small amount of dichloromethane was added
  21. temperaturethe mixture was heated to 60° C.
  22. dissolutionto dissolve the powder completely
  23. waitThe resultant solution was left
  24. waitto stand for 1 hour at room temperature
  25. waitleft
  26. waitto stand for 13 hours at −20° C
  27. customCrystals precipitated
  28. washwere washed 3 times with 10 mL of hexane

Sources & evidence

ORD record
ord-3f73a677c4cc4809911f5eb18aa7d0b1
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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