1,3-Dimethyl-2-imidazolidinone → Di(p-chlorophenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)methane

HRID 1050668Notes

Reaction equation

HRID 1050668 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.CN1CCN(C)C1=O.[Cl:43][C:44]1[CH:49]=[CH:48][C:47]([C:50]([C:56]2[CH:61]=[CH:60][C:59]([Cl:62])=[CH:58][CH:57]=2)=[C:51]2[CH:55]=[CH:54][CH:53]=[CH:52]2)=[CH:46][CH:45]=1>O1CCCC1.CCCCCC>[Cl:43][C:44]1[CH:45]=[CH:46][C:47]([C:50]([C:56]2[CH:57]=[CH:58][C:59]([Cl:62])=[CH:60][CH:61]=2)([CH:51]2[CH:52]=[CH:53][CH:54]=[CH:55]2)[C:7]2([CH3:30])[C:6]3[C:5]([CH3:23])([CH:12]4[CH2:13][CH2:14][CH:15]=[CH:16][C:11]4=[C:10]4[C:18]=3[CH2:17][C:19]3[CH:20]=[CH:21][CH:22]=[CH:8][C:9]4=3)[C:4]([CH3:26])([CH3:25])[C:3]([CH3:28])([CH3:27])[C:2]2([CH3:1])[CH3:29])=[CH:48][CH:49]=1

Participants

7

Reactant 4

HCID 66611,3-Dimethyl-2-imidazolidinoneHCID 118334636,6-Di(p-chlorophenyl)fulveneHCID 86606716OctamethyloctahydrodibenzofluoreneHCID 178418339Butyllithium

Product 1

HCID 131729404Di(p-chlorophenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)methane

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

A reaction vessel equipped with a dropping funnel was charged with 40 ml of dehydrated tetrahydrofuran and 2.35 g (6.08 mmol) of octamethyloctahydrodibenzofluorene synthesized in Synthesis Example 2-1 under a nitrogen atmosphere. Then, 4.62 ml (7.30 mmol) of a 1.58 mol/L hexane solution of n-butyllithium was slowly added dropwise and while cooling this solution to 0° C., and the mixture was stirred. Then, 0.86 ml (7.90 mmol) of 1,3-dimethyl-2-imidazolidinone was added to the solution and the mixture was stirred for 30 minutes. Subsequently, the dropping funnel was charged with a solution prepared by dissolving 2.00 g (6.68 mmol) of 6,6-di{p-chlorophenyl}fulvene in 30 ml of dehydrated tetrahydrofuran. The solution was slowly added dropwise while cooling the solution to −78° C. The mixture was stirred for one day while returning the temperature thereof slowly to room temperature. This reaction solution was subjected to extraction with diethyl ether. The organic layer was washed with 1 N hydrochloric acid, a saturated aqueous solution of sodium hydrogen carbonate and saturated brine. The organic phase collected by separation was dried over anhydrous magnesium sulfate and magnesium sulfate was separated by filtration. The filtrate was subjected to distillation under reduced pressure using a rotary evaporator to remove the solvent. The residue was purified by using a silica gel column and recrystallized from toluene to obtain a target product (yield 0.714 g (17%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. customA reaction vessel equipped with a dropping funnel
  2. customsynthesized in Synthesis Example 2-1 under a nitrogen atmosphere
  3. stirringthe mixture was stirred for 30 minutes
  4. additionSubsequently, the dropping funnel was charged with a solution
  5. customprepared
  6. additionThe solution was slowly added dropwise
  7. temperaturewhile cooling the solution to −78° C
  8. stirringThe mixture was stirred for one day
  9. customslowly to room temperature
  10. extractionThis reaction solution was subjected to extraction with diethyl ether
  11. washThe organic layer was washed with 1 N hydrochloric acid
  12. customThe organic phase collected by separation
  13. dry with materialwas dried over anhydrous magnesium sulfate and magnesium sulfate
  14. customwas separated by filtration
  15. distillationThe filtrate was subjected to distillation under reduced pressure
  16. customa rotary evaporator
  17. customto remove the solvent
  18. customThe residue was purified
  19. customrecrystallized from toluene
  20. customto obtain a target product (yield 0.714 g (17%))

Sources & evidence

ORD record
ord-7dc229ecb7294af3b5374b3f2e5931d3
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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