Hydrochloric Acid → Bis(4-[p-trifluoromethylphenyl]-phenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)methane

HRID 1050673Notes

Reaction equation

HRID 1050673 reaction equation
[CH3:1][C:2]1([CH3:29])[CH:7]2[CH:8]3[CH2:22][CH2:21][CH:20]=[CH:19][C:9]3=[C:10]3[C:18]([CH2:17][C:16]4[CH:15]=[CH:14][CH:13]=[CH:12][C:11]3=4)=[C:6]2[C:5](C)([CH3:23])[C:4]([CH3:26])([CH3:25])[C:3]1([CH3:28])[CH3:27].[CH2:30]([Li])CCC.[F:35][C:36]([F:72])([F:71])[C:37]1[CH:42]=[CH:41][C:40]([C:43]2[CH:48]=[CH:47][C:46]([C:49]([C:55]3[CH:60]=[CH:59][C:58]([C:61]4[CH:66]=[CH:65][C:64]([C:67]([F:70])([F:69])[F:68])=[CH:63][CH:62]=4)=[CH:57][CH:56]=3)=[C:50]3[CH:54]=[CH:53][CH:52]=[CH:51]3)=[CH:45][CH:44]=2)=[CH:39][CH:38]=1.Cl>CCCCCC.COC(C)(C)C>[F:35][C:36]([F:71])([F:72])[C:37]1[CH:42]=[CH:41][C:40]([C:43]2[CH:48]=[CH:47][C:46]([C:49]([C:55]3[CH:60]=[CH:59][C:58]([C:61]4[CH:62]=[CH:63][C:64]([C:67]([F:70])([F:68])[F:69])=[CH:65][CH:66]=4)=[CH:57][CH:56]=3)([CH:50]3[CH:51]=[CH:52][CH:53]=[CH:54]3)[C:7]3([CH3:30])[C:6]4[C:5]([CH3:23])([CH:12]5[CH2:13][CH2:14][CH:15]=[CH:16][C:11]5=[C:10]5[C:18]=4[CH2:17][C:19]4[CH:20]=[CH:21][CH:22]=[CH:8][C:9]5=4)[C:4]([CH3:26])([CH3:25])[C:3]([CH3:28])([CH3:27])[C:2]3([CH3:1])[CH3:29])=[CH:45][CH:44]=2)=[CH:39][CH:38]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 86606716OctamethyloctahydrodibenzofluoreneHCID 866232016,6-Bis(4-(p-trifluoromethylphenyl)-phenyl)fulveneHCID 178418339Butyllithium

Product 1

HCID 131736086Bis(4-[p-trifluoromethylphenyl]-phenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)methane

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
0 °C

Procedure

Under a nitrogen atmosphere, 0.81 g (2.20 mmol) of octamethyloctahydrodibenzofluorene and 100 ml of dehydrated tert-butyl methyl ether were added, and the mixture was stirred. This solution was cooled to 0° C., and 1.59 ml (2.42 mmol) of a 1.52 mol/l hexane solution of n-butyllithium was added. Subsequently, the mixture was stirred at room temperature for 24 hours. The resulting solution was cooled to −78° C., and 1.04 g (2 mmol) of 6,6-bis(4-(p-trifluoromethylphenyl)-phenyl)fulvene was added. The mixture was stirred at room temperature for 3 hours. When the completion of reaction was checked, 1 N hydrochloric acid was added to the reaction solution to perform liquid-liquid phase separation. The aqueous layer was subjected to extraction with diethyl ether two times, and the extract was combined with the organic layer previously obtained. The liquid was washed with a saturated aqueous solution of sodium hydrogen carbonate, water and saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and the residue was subjected to separation by silica gel chromatography to obtain a target product (yield 0.92 g (47%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. stirringSubsequently, the mixture was stirred at room temperature for 24 hours
  2. temperatureThe resulting solution was cooled to −78° C.
  3. stirringThe mixture was stirred at room temperature for 3 hours
  4. customWhen the completion of reaction
  5. customliquid-liquid phase separation
  6. extractionThe aqueous layer was subjected to extraction with diethyl ether two times
  7. custompreviously obtained
  8. washThe liquid was washed with a saturated aqueous solution of sodium hydrogen carbonate, water and saturated brine
  9. dry with materialdried over magnesium sulfate
  10. distillationThe solvent was distilled off
  11. customthe residue was subjected to separation by silica gel chromatography
  12. customto obtain a target product (yield 0.92 g (47%))

Sources & evidence

ORD record
ord-3af8724066374231947e80191ae7b60b
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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