Diethyl Ether → HCID 178424130, compound

HRID 1050664Notes

Reaction equation

HRID 1050664 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][C:34]=2[CH3:39])=[CH:23]3)=[C:19](C2C=CC=C2)[C:18]([C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][C:46]=2[CH3:51])=[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:50]=[CH:49][CH:48]=[CH:47][C:46]=4[CH3:51])[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:38]=[CH:37][CH:36]=[CH:35][C:34]=1[CH3:39])[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 131736082HCID 131736082, compoundHCID 178418339Butyllithium

Product 1

HCID 178424130HCID 178424130, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

Under a nitrogen atmosphere, a 50-mL Schlenk flask was charged with 0.36 g (0.50 mmol) of dibenzylmethylene(cyclopentadienyl)(2,7-di[o-tolyl]-3,6-ditert-butylfluorene) and 25 mL of dehydrated diethyl ether, and the mixture was stirred. This mixed slurry solution was cooled in an ice bath, 0.72 mL (1.09 mmol) of a 1.52 mol/L hexane solution of n-butyllithium was added, and the mixture was stirred for 40 hours while gradually warming to room temperature. This red reaction solution was cooled to −78° C. in a dry ice/methanol bath, and then 0.251 g (1.08 mmol) of zirconium tetrachloride was added. Subsequently, the mixture was stirred for 17 hours while gradually warming to room temperature to obtain a red-orange suspension. The solvent was dried 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 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/cold n-pentane and dried to obtain a target product as a dark pink powder (yield 167 mg (38%)). 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 40 hours
  3. temperatureThis red reaction solution was cooled to −78° C. in a dry ice/methanol bath
  4. stirringSubsequently, the mixture was stirred for 17 hours
  5. temperaturewhile gradually warming to room temperature
  6. customto obtain a red-orange suspension
  7. customThe solvent was dried 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/cold n-pentane
  16. customdried

Sources & evidence

ORD record
ord-2bae1b19cd744e55a758348bd92cb8c7
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

Loading…