Diethyl Ether → HCID 178440565, compound

HRID 1050656Notes

Reaction equation

HRID 1050656 reaction equation
C1(=[C:7]2[C:19]3[C:11]([CH:12]=[C:13]4[C:18]=3[CH:17]=[C:16]([C:20]([CH3:23])([CH3:22])[CH3:21])[C:15]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)=[CH:14]4)=[C:10](C3C=CC=C3)[C:9]([C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=3)=[C:8]2[C:41]([CH3:44])([CH3:43])[CH3:42])CCCCC1.C(O[CH2:48][CH3:49])C.[CH2:50]([Li])[CH2:51][CH2:52]C.[Cl-:55].[Cl-].[Cl-].[Cl-].[Zr+4:59].[CH3:60][CH2:61][CH2:62][CH2:63][CH2:64][CH3:65]>>[Cl-:55].[Cl-:55].[C:62]1(=[Zr+2:59]([CH:49]2[CH:48]=[CH:52][CH:51]=[CH:50]2)[C:10]2[C:11]3[CH2:12][C:13]4[C:18](=[CH:17][C:16]([C:20]([CH3:21])([CH3:22])[CH3:23])=[C:15]([C:24]5[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=5)[CH:14]=4)[C:19]=3[CH:7]=[C:8]([C:41]([CH3:44])([CH3:42])[CH3:43])[C:9]=2[C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[CH2:61][CH2:60][CH2:65][CH2:64][CH2:63]1

Participants

6

Reactant 5

HCID 3283Diethyl EtherHCID 8058HexaneHCID 9856075Zirconium chloride (ZrCl4), (T-4)-HCID 131736075Cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorene)HCID 178418339Butyllithium

Product 1

HCID 178440565HCID 178440565, compoundYield 57%

Conditions

Temperature
0 °C

Procedure

Under a nitrogen atmosphere, a 100-mL Schlenk flask was charged with 0.98 g (1.70 mmol) of cyclohexylidene(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 to 0° C. in an ice bath, and 2.40 mL (3.74 mmol) of a 1.56 mol/L hexane solution of n-butyllithium was added. The mixture was stirred for 23 hours while gradually warming to room temperature. This red reaction solution was cooled to −78° C. in a dry ice/methanol bath, and then 0.391 g (1.68 mmol) of zirconium tetrachloride was added. Subsequently, the mixture was stirred for 22 hours while gradually warming to room temperature to obtain an orange 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, and insolubles were washed with n-hexane, and the red powders 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 cold diethyl ether/cold n-hexane to obtain a target product as an orange solid (yield 0.71 g (57%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. stirringThe mixture was stirred for 23 hours
  2. temperaturewhile gradually warming to room temperature
  3. temperatureThis red reaction solution was cooled to −78° C. in a dry ice/methanol bath
  4. stirringSubsequently, the mixture was stirred for 22 hours
  5. temperaturewhile gradually warming to room temperature
  6. customto obtain an 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, and insolubles
  11. washwere washed with n-hexane
  12. extractionthe red powders 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 cold diethyl ether/cold n-hexane

Sources & evidence

ORD record
ord-c15cb12748f0418eaebf97cc0af20a9d
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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