Diethyl Ether → HCID 178423637, compound

HRID 1050662Notes

Reaction equation

HRID 1050662 reaction equation
C(C(=[C:16]1[C:28]2[C:20]([CH:21]=[C:22]3[C:27]=2[CH:26]=[C:25]([C:29]([CH3:32])([CH3:31])[CH3:30])[C:24]([C:33]2[CH:38]=[CH:37][C:36]([CH3:39])=[CH:35][CH:34]=2)=[CH:23]3)=[C:19](C2C=CC=C2)[C:18]([C:45]2[CH:50]=[CH:49][C:48]([CH3:51])=[CH:47][CH:46]=2)=[C:17]1[C:52]([CH3:55])([CH3:54])[CH3:53])CC1C=CC=CC=1)C1C=CC=CC=1.C(O[CH2:59][CH3:60])C.[CH2:61]([Li])[CH2:62][CH2:63][CH3:64].[Cl-:66].[Cl-].[Cl-].[Cl-].[Zr+4:70]>CCCCCC>[Cl-:66].[Cl-:66].[CH2:61]([C:53](=[Zr+2:70]([CH:60]1[CH:59]=[CH:33][CH:24]=[CH:25]1)[C:23]1[C:22]2[CH2:21][C:20]3[C:28](=[CH:16][C:17]([C:52]([CH3:55])([CH3:53])[CH3:54])=[C:18]([C:45]4[CH:46]=[CH:47][C:48]([CH3:51])=[CH:49][CH:50]=4)[CH:19]=3)[C:27]=2[CH:26]=[C:25]([C:29]([CH3:32])([CH3:31])[CH3:30])[C:24]=1[C:33]1[CH:34]=[CH:35][C:36]([CH3:39])=[CH:37][CH:38]=1)[CH2:52][C:17]1[CH:16]=[CH:28][CH:20]=[CH:19][CH:18]=1)[C:62]1[CH:23]=[CH:22][CH:21]=[CH:64][CH:63]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 9856075Zirconium chloride (ZrCl4), (T-4)-HCID 131736079Dibenzylmethylene(cyclopentadienyl)(2,7-di[p-tolyl]-3,6-ditert-butylfluorene)HCID 178418339Butyllithium

Product 1

HCID 178423637HCID 178423637, compoundYield 58%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

Under a nitrogen atmosphere, a 100-mL Schlenk flask was charged with 1.04 g (1.45 mmol) of dibenzylmethylene(cyclopentadienyl)(2,7-di[p-tolyl]-3,6-ditert-butylfluorene) and 60 mL of dehydrated diethyl ether, and the mixture was stirred. This mixed slurry solution was cooled in an ice bath, and 2.00 mL (3.20 mmol) of a 1.60 mol/L hexane solution of n-butyllithium was added. The mixture was stirred for 51 hours while gradually warming to room temperature. This red-orange reaction solution was cooled to −78° C. in a dry ice/methanol bath, and then 0.363 g (1.60 mmol) of zirconium tetrachloride was added. Subsequently, the mixture was stirred for 43 hours while gradually warming to room temperature to obtain an orange colored suspension. The solvent was removed by distillation under reduced pressure. Under a nitrogen atmosphere, the residue was dissolved in n-hexane, the liquid was passed through a glass filter filled with Celite, insolubles were washed with n-hexane, and the orange powder insoluble in n-hexane was subjected to extraction with dichloromethane. The solvent in which the dichloromethane-solubles were dissolved was distilled off. The residue was washed with diethyl ether/n-hexane to obtain a target product as an orange powder (yield 744 mg (58%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. temperatureThis mixed slurry solution was cooled in an ice bath
  2. stirringThe mixture was stirred for 51 hours
  3. temperatureThis red-orange reaction solution was cooled to −78° C. in a dry ice/methanol bath
  4. stirringSubsequently, the mixture was stirred for 43 hours
  5. temperaturewhile gradually warming to room temperature
  6. customto obtain an orange colored suspension
  7. customThe solvent was removed by distillation under reduced pressure
  8. dissolutionUnder a nitrogen atmosphere, the residue was dissolved in n-hexane
  9. filtrationfilter
  10. additionfilled with Celite, insolubles
  11. washwere washed with n-hexane
  12. extractionthe orange powder insoluble in n-hexane was subjected to extraction with dichloromethane
  13. dissolutionThe solvent in which the dichloromethane-solubles were dissolved
  14. distillationwas distilled off
  15. washThe residue was washed with diethyl ether/n-hexane

Sources & evidence

ORD record
ord-4df8fbade24d4ce7a0343dbb1b906fff
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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