Diethyl Ether → HCID 178440564, compound

HRID 1050659Notes

Reaction equation

HRID 1050659 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:42]=[CH:41][C:40]4[C:35](=[CH:36][CH:37]=[CH:38][CH:39]=4)[CH:34]=2)=[CH:23]3)=[C:19](C2C=CC=C2)[C:18]([C:48]2[CH:57]=[CH:56][C:55]3[C:50](=[CH:51][CH:52]=[CH:53][CH:54]=3)[CH:49]=2)=[C:17]1[C:58]([CH3:61])([CH3:60])[CH3:59])CC1C=CC=CC=1)C1C=CC=CC=1.C(O[CH2:65][CH3:66])C.[CH2:67]([Li])[CH2:68][CH2:69][CH3:70].[Cl-:72].[Cl-].[Cl-].[Cl-].[Zr+4:76]>CCCCCC>[Cl-:72].[Cl-:72].[CH2:67]([C:59](=[Zr+2:76]([CH:66]1[CH:65]=[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:42]=[CH:41][C:40]5[C:35](=[CH:36][CH:37]=[CH:38][CH:39]=5)[CH:34]=4)[CH:23]=3)[C:28]=2[CH:16]=[C:17]([C:58]([CH3:61])([CH3:60])[CH3:59])[C:18]=1[C:48]1[CH:57]=[CH:56][C:55]2[C:50](=[CH:51][CH:52]=[CH:53][CH:54]=2)[CH:49]=1)[CH2:58][C:17]1[CH:16]=[CH:28][CH:20]=[CH:19][CH:18]=1)[C:68]1[CH:23]=[CH:22][CH:21]=[CH:70][CH:69]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 9856075Zirconium chloride (ZrCl4), (T-4)-HCID 131736077Dibenzylmethylene(cyclopentadienyl)(2,7-di[2-naphthyl]-3,6-ditert-butylfluorene)HCID 178418339Butyllithium

Product 1

HCID 178440564HCID 178440564, compoundYield 49%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

Under a nitrogen atmosphere, a 100-mL Schlenk flask was charged with 0.64 g (0.811 mmol) of dibenzylmethylene(cyclopentadienyl)(2,7-di[2-naphthyl]-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, 1.14 mL (1.82 mmol) of a 1.60 mol/L hexane solution of n-butyllithium was added. The mixture was stirred for 42 hours while gradually warming to room temperature. This red reaction solution was cooled to −78° C. in a dry ice/methanol bath, and then 0.180 g (0.772 mmol) of zirconium tetrachloride was added. Subsequently, the mixture was stirred for 47 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, and the liquid was passed through a glass filter filled with Celite, insolubles were washed with n-hexane, and the red 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 a red-orange powder (yield 379 mg (49%)). 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 42 hours
  3. temperatureThis red reaction solution was cooled to −78° C. in a dry ice/methanol bath
  4. stirringSubsequently, the mixture was stirred for 47 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 red 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-689186ab39c144d1b2fdbbc887a1a71d
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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