Hydrochloric Acid → HCID 131736074, compound

HRID 1050653Notes

Reaction equation

HRID 1050653 reaction equation
[CH3:1][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]([CH3:23])=[C:9]([C:19]([CH3:22])([CH3:21])[CH3:20])[CH:10]=3)[CH2:5][C:4]=2[CH:3]=1.[CH2:24]([Li])[CH2:25][CH2:26][CH3:27].[CH2:29]([C:33]([CH2:39][CH2:40][CH2:41][CH3:42])=C1C=CC=C1)[CH2:30][CH2:31][CH3:32].Cl.O1CCC[CH2:45]1>C(OCC)C.CCCCCC>[CH2:39]([C:33]([CH2:29][CH2:30][CH2:31][CH3:32])=[C:10]1[C:11]2[C:6]([CH:5]=[C:4]3[C:12]=2[CH:13]=[C:14]([C:15]([CH3:16])([CH3:17])[CH3:18])[C:2]([CH3:1])=[CH:3]3)=[C:7]([CH:24]2[CH:45]=[CH:27][CH:26]=[CH:25]2)[C:8]([CH3:23])=[C:9]1[C:19]([CH3:22])([CH3:21])[CH3:20])[CH2:40][CH2:41][CH3:42]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8028Tetrahydrofuran2×HCID 190333046,6-Di(n-butyl)fulveneHCID 219826932,7-Dimethyl-3,6-ditert-butyl-fluoreneHCID 178418339Butyllithium

Product 1

HCID 131736074HCID 131736074, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

Under a nitrogen atmosphere, dehydrated tetrahydrofuran was added to 0.783 g (2.55 mmol) of 2,7-dimethyl-3,6-ditert-butyl-fluorene, and the mixture was stirred. This solution was cooled in an ice bath, and 1.85 mL (2.85 mmol) of a 1.54 mol/L hexane solution of n-butyllithium was added. The mixture was stirred at room temperature for 2 hours. The resulting orange-colored solution was cooled to −78° C. in a dry ice/methanol bath, and a solution prepared by dissolving 0.571 g (3.00 mmol) of 6,6-di(n-butyl)fulvene synthesized in Synthesis Example 1-2 (i) in 15 mL of dehydrated tetrahydrofuran was added dropwise over 20 minutes, and the mixture was stirred for 2 hours. 100 mL of 1 N hydrochloric acid was added to the resulting orange-colored solution to terminate the reaction. 100 mL of diethyl ether was added to perform liquid-liquid phase separation, and the soluble fraction was extracted. This organic layer was 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. The solvent was distilled off, and the residue was recrystallized from diethyl ether/methanol to obtain a target product as a white powder (yield 0.63 g (50%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. temperatureThis solution was cooled in an ice bath
  2. stirringThe mixture was stirred at room temperature for 2 hours
  3. customa solution prepared
  4. additionwas added dropwise over 20 minutes
  5. stirringthe mixture was stirred for 2 hours
  6. customto terminate
  7. customthe reaction
  8. customliquid-liquid phase separation
  9. extractionthe soluble fraction was extracted
  10. washThis organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  11. dry with materialonce with saturated brine, and dried over magnesium sulfate
  12. distillationThe solvent was distilled off
  13. customthe residue was recrystallized from diethyl ether/methanol

Sources & evidence

ORD record
ord-216373389588499c97c02d83887b653f
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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