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

HRID 420025

Reaktionsgleichung

Reaktionsgleichung von HRID 420025
[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

Komponenten

6

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  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.

Quellen und Nachweise

ORD-Eintrag
ord-97acc016e3884f66bfc9c75bf2b3e773
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08093418B2

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