1,3-Cyclopentadiene, 5-(1-methylethylidene)- → (Cyclopentadienyl)-[(2,7-di-phenyl-3,6-di-tert-butylfluorenyl)]-propane

HRID 2056788Notes

Reaction equation

HRID 2056788 reaction equation
[CH2:1]([Li])CCC.[C:6]1([C:12]2[C:24]([C:25]([CH3:28])([CH3:27])[CH3:26])=[CH:23][C:22]3[C:21]4[C:16](=[CH:17][C:18]([C:33]5[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=5)=[C:19]([C:29]([CH3:32])([CH3:31])[CH3:30])[CH:20]=4)[CH2:15][C:14]=3[CH:13]=2)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C[C:40]([CH3:46])=[C:41]1[CH:45]=[CH:44][CH:43]=[CH:42]1>C1COCC1.CCOCC>[CH:41]1([CH:40]([C:13]2[C:14]3[CH2:15][C:16]4[C:21](=[CH:20][C:19]([C:29]([CH3:31])([CH3:32])[CH3:30])=[C:18]([C:33]5[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=5)[CH:17]=4)[C:22]=3[CH:23]=[C:24]([C:25]([CH3:26])([CH3:27])[CH3:28])[C:12]=2[C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=2)[CH2:46][CH3:1])[CH:42]=[CH:43][CH:44]=[CH:45]1

Participants

6

Reactant 3

HCID 1374671,3-Cyclopentadiene, 5-(1-methylethylidene)-HCID 219826953,6-DI-Tert-butyl-2,7-diphenyl-9H-fluoreneHCID 178418339Butyllithium

Product 1

HCID 131726780(Cyclopentadienyl)-[(2,7-di-phenyl-3,6-di-tert-butylfluorenyl)]-propane

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

Butyllithium (1.5 ml, 1.6M in hexane, 2.40 mmol) was added to 2,7-diphenyl-3,6-di-t-butyl-fluorene (0.95 g, 2.20 mmol) in THF (20 ml) at −78° C. The reaction mixture was allowed to warm to room temperature and stirred for 2.5 hours. The solvent was removed under vacuum. Ether (5 ml) was added and removed under vacuum. Ether (25 ml) was added and 6,6′-dimethylfulvene (0.23 g, 2.43 mmol) in ether (5 ml) was added to the reaction mixture at 0° C. The reaction was stirred at room temperature for 5 days. The reaction mixture was quenched with water, extracted with ether, dried over MgSO4, and evaporated under vacuum to afford the residue which was purified by column chromatography (silica gel, hexane/CH2Cl2=5/1) and crystallized from hot hexane. The yield was 0.40 g, 34%. 1H NMR (CDCl3): δ 7.91 and 7.30 (each s, 2H, 1,8- and 4,5-H (Flu), 7.35 (m, 10H, Ph), 6.76, 6.40 (m, 3H, Cp), 4.04 and 4.02 (s, 2H, H9), 3.00 and 2.78 (br s, 2H, CH2 Cp), 1.31 (s, 18H, t-Bu), 1.11 and 1.09 (s, 6H, Me). 1H NMR (CD2Cl2): δ 7.91 and 7.29 (each s, 2H, 1,8- and 4,5-H (Flu), 7.2-7.4 (m, 10H, Ph), 6.8-6.7, 6.40 (m, 3H, Cp), 4.02 (brs, 2H, H9), 3.00 and 2.78 (br s, 2H, CH2 Cp), 1.28 (s, 18H, t-Bu), 1.07 and 1.04 (s, 6H, Me). HPLC: 10.38 and 10.65 min.

Workup

  1. customThe solvent was removed under vacuum
  2. additionEther (5 ml) was added
  3. customremoved under vacuum
  4. additionEther (25 ml) was added
  5. stirringThe reaction was stirred at room temperature for 5 days
  6. customThe reaction mixture was quenched with water
  7. extractionextracted with ether
  8. dry with materialdried over MgSO4
  9. customevaporated under vacuum
  10. customto afford the residue which
  11. customwas purified by column chromatography (silica gel, hexane/CH2Cl2=5/1)
  12. customcrystallized from hot hexane
  13. custom10.38 and 10.65 min.

Sources & evidence

ORD record
ord-b63efd58c56241ad937be8a37002b446
Source dataset
uspto-grants-2008_02
Patent number
US07335711B2

Reaction notes

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