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

HRID 420025

반응식

HRID 420025 반응식
[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

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매

실험 절차

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.

후처리

  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.

출처 및 근거

ORD 기록
ord-97acc016e3884f66bfc9c75bf2b3e773
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08093418B2

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