Diethyl Ether → HCID 178440566, compound

HRID 1050649Notes

Reaction equation

HRID 1050649 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][CH:36]=[CH:35][CH:34]=2)=[CH:23]3)=[C:19](C2C=CC=C2)[C:18]([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)=[C:17]1[C:50]([CH3:53])([CH3:52])[CH3:51])CC1C=CC=CC=1)C1C=CC=CC=1.C(O[CH2:57][CH3:58])C.[CH2:59]([Li])[CH2:60][CH2:61][CH3:62].[Cl-:64].[Cl-].[Cl-].[Cl-].[Zr+4:68]>CCCCCC>[Cl-:64].[Cl-:64].[CH2:59]([C:51](=[Zr+2:68]([CH:58]1[CH:57]=[CH:33][CH:24]=[CH:25]1)[C:19]1[C:20]2[CH2:21][C:22]3[C:27](=[CH:26][C:25]([C:29]([CH3:30])([CH3:31])[CH3:32])=[C:24]([C:33]4[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=4)[CH:23]=3)[C:28]=2[CH:16]=[C:17]([C:50]([CH3:53])([CH3:52])[CH3:51])[C:18]=1[C:44]1[CH:45]=[CH:46][CH:47]=[CH:48][CH:49]=1)[CH2:50][C:17]1[CH:16]=[CH:28][CH:20]=[CH:19][CH:18]=1)[C:60]1[CH:23]=[CH:22][CH:21]=[CH:62][CH:61]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 9856075Zirconium chloride (ZrCl4), (T-4)-HCID 131736072HCID 131736072, compoundHCID 178418339Butyllithium

Product 1

HCID 178440566HCID 178440566, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

Under a nitrogen atmosphere, a 100-mL Schlenk flask was charged with 0.59 g (0.855 mmol) of dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorene) and 40 mL of dehydrated diethyl ether, and the mixture was stirred. This mixed slurry solution was cooled in an ice bath, and 1.21 mL (1.88 mmol) of a 1.56 mol/L hexane solution of n-butyllithium was added. The mixture was stirred for 45 hours while gradually warming to room temperature. The resulting red reaction solution was cooled to −78° C. in a dry ice/methanol bath, and then 0.200 g (0.858 mmol) of zirconium tetrachloride was added. Subsequently, the mixture was stirred for 42 hours while gradually warming to room temperature to obtain a red-orange suspension. The solvent was removed by distillation under reduced pressure. Under a nitrogen atmosphere, the residue was dissolved in n-hexane, and the liquid was passed through a glass filter filled with Celite, insolubles were washed n-hexane, and the orange colored 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/cold n-pentane and dried to obtain a target product as an orange-colored powder (yield 515 mg (71%)). 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 45 hours
  3. temperatureThe resulting red reaction solution was cooled to −78° C. in a dry ice/methanol bath
  4. stirringSubsequently, the mixture was stirred for 42 hours
  5. temperaturewhile gradually warming to room temperature
  6. customto obtain a red-orange 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 n-hexane
  12. extractionthe orange colored 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/cold n-pentane
  16. customdried

Sources & evidence

ORD record
ord-9e703c60a2174fa5bc718a9571d9412b
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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