Hydrochloric Acid → HCID 86623194, compound

HRID 1050660Notes

Reaction equation

HRID 1050660 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.[CH3:24][C:25]1[CH:30]=[CH:29][C:28](OB(O)O)=[CH:27][CH:26]=1.C(=O)([O-])[O-].[Na+].[Na+].Cl>C(O)C.CCCCCC.ClCCl.COCCOC>[C:4]1([CH3:5])[CH:12]=[CH:13][C:14]([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:28]5[CH:29]=[CH:30][C:25]([CH3:24])=[CH:26][CH:27]=5)=[C:9]([C:19]([CH3:21])([CH3:20])[CH3:22])[CH:8]=4)[CH2:5][C:4]=3[CH:12]=2)=[CH:2][CH:3]=1

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 135475422,7-Dibromo-3,6-DI-tert-butyl-9H-fluoreneHCID 190353504-Methylphenyl dihydrogen borate

Product 1

HCID 86623194HCID 86623194, compoundYield 165.6%

Reagents, catalysts & solvents 4

HCID 702EthanolSolvent2×HCID 6344DichloromethaneSolventHCID 8058HexaneSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

Under a nitrogen atmosphere, 120 mL of dehydrated 1,2-dimethoxyethane was added to 8.00 g (18.3 mmol) of 2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis Example 1-1(i) and 1.05 g (0.909 mmol) of Pd(PPh3), and the mixture was stirred at room temperature for 20 minutes. To this solution, a solution prepared by dissolving 5.50 g (40.5 mmol) of 4-methylphenylboric acid in 20 mL of ethanol was added. The mixture was stirred at room temperature for 20 minutes, and then 36.8 mL (73.6 mmol) of a 2.0 mol/L aqueous solution of sodium carbonate was added. Subsequently, the mixture was heated to reflux for 21 hours, left to be naturally cooled, and then 1N hydrochloric acid was added in an ice bath to terminate the reaction. Dichloromethane was then added to perform a liquid-liquid phase separation, and the aqueous layer was subjected to extraction with diethyl ether twice. The resultant was combined with the organic layer obtained previously. The resultant liquid was then 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. Subsequently, the solvent was distilled off, and the resultant was subjected to separation by silica gel chromatography. To the whitish yellow powder obtained, small amount of a mixed solution of n-hexane and ethanol was added. The mixture was heated to 65° C., and then was left to stand for 1 hour at room temperature. Crystals Precipitated were washed 10 times with 2 mL of cold methanol and 20 times with 1 mL of cold n-hexane to obtain a target product as a white powder (yield 6.95 g (83%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. customTo this solution, a solution prepared
  2. additionwas added
  3. stirringThe mixture was stirred at room temperature for 20 minutes
  4. temperatureSubsequently, the mixture was heated
  5. temperatureto reflux for 21 hours
  6. waitleft
  7. temperatureto be naturally cooled
  8. customto terminate
  9. customthe reaction
  10. customa liquid-liquid phase separation
  11. extractionthe aqueous layer was subjected to extraction with diethyl ether twice
  12. customobtained previously
  13. washThe resultant liquid was then washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  14. dry with materialonce with saturated brine, and then dried over magnesium sulfate
  15. distillationSubsequently, the solvent was distilled off
  16. customthe resultant was subjected to separation by silica gel chromatography
  17. customTo the whitish yellow powder obtained
  18. temperatureThe mixture was heated to 65° C.
  19. waitwas left
  20. waitto stand for 1 hour at room temperature
  21. customCrystals Precipitated
  22. washwere washed 10 times with 2 mL of cold methanol and 20 times with 1 mL of cold n-hexane

Sources & evidence

ORD record
ord-6529e6958e96493aac9697458bd903a9
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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