Hydrochloric Acid → Cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorene)

HRID 1050655Notes

Reaction equation

HRID 1050655 reaction equation
[C:1]1([C:7]2[C:19]([C:20]([CH3:23])([CH3:22])[CH3:21])=[CH:18][C:17]3[C:16]4[C:11](=[CH:12][C:13]([C:28]5[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=5)=[C:14]([C:24]([CH3:27])([CH3:26])[CH3:25])[CH:15]=4)[CH2:10][C:9]=3[CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39].C1([C:46]2[C:50](=C)[CH:49]=[CH:48][CH:47]=2)CCCCC1.Cl>O1CCCC1.C(OCC)C>[C:36]1(=[C:15]2[C:16]3[C:11]([CH:10]=[C:9]4[C:17]=3[CH:18]=[C:19]([C:20]([CH3:21])([CH3:22])[CH3:23])[C:7]([C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)=[CH:8]4)=[C:12]([CH:49]3[CH:48]=[CH:47][CH:46]=[CH:50]3)[C:13]([C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)=[C:14]2[C:24]([CH3:26])([CH3:27])[CH3:25])[CH2:35][CH2:34][CH2:39][CH2:38][CH2:37]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8058HexaneHCID 219826953,6-DI-Tert-butyl-2,7-diphenyl-9H-fluoreneHCID 22327799Cyclohexylfulvene

Product 1

HCID 131736075Cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorene)Yield 64%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Under a nitrogen atmosphere, 30 mL of dehydrated tetrahydrofuran was added to 1.14 g (2.65 mmol) of 2,7-diphenyl-3,6-ditert-butyl-fluorene synthesized in Synthesis Example 1-1 (ii), and the mixture was stirred. This solution was cooled in an ice bath, and 1.90 mL (2.96 mmol) of a 1.56 mol/L hexane solution n-butyllithium was added. The mixture was stirred at room temperature for 2 hours. The resulting dark red solution was cooled to −78° C. in a dry ice/methanol bath, and a solution prepared by dissolving 0.49 g (3.35 mmol) of cyclohexylfulvene, which was synthesized according to a method described in JP-A No. 2000-26490, in 20 mL of tetrahydrofuran was added dropwise over 15 minutes. Subsequently, the mixture was stirred for 19 hours while gradually warming to room temperature. 30 mL of 1 N hydrochloric acid was added to the resulting dark red 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 with diethylether and methanol to obtain a target product as a pale yellow powder (yield 0.98 g (64%)). 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. customwas synthesized
  5. stirringSubsequently, the mixture was stirred for 19 hours
  6. temperaturewhile gradually warming to room temperature
  7. customto terminate
  8. customthe reaction
  9. customliquid-liquid phase separation
  10. extractionthe soluble fraction was extracted
  11. washThis organic layer was washed two times with a saturated aqueous solution of sodium hydrogen carbonate, two times with water
  12. dry with materialonce with saturated brine, and dried over magnesium sulfate
  13. distillationThe solvent was distilled off
  14. customthe residue was recrystallized with diethylether and methanol

Sources & evidence

ORD record
ord-43f72d7d574240ce907a09ba378b7cec
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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