Chlorotrimethylsilane → (7-Bromo-9,9-dioctyl-9H-fluoren-2-yl)(trimethyl)silane

HRID 1243128Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1243128
C([Li])CCC.CCCCCC.[Br:12][C:13]1[CH:25]=[CH:24][C:23]2[C:22]3[C:17](=[CH:18][C:19](Br)=[CH:20][CH:21]=3)[C:16]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42])([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[C:15]=2[CH:14]=1.Cl[Si:44]([CH3:47])([CH3:46])[CH3:45]>C1COCC1>[Br:12][C:13]1[CH:25]=[CH:24][C:23]2[C:22]3[C:17](=[CH:18][C:19]([Si:44]([CH3:47])([CH3:46])[CH3:45])=[CH:20][CH:21]=3)[C:16]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42])([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[C:15]=2[CH:14]=1

Komponenten

6

Edukt 4

HCID 6397ChlorotrimethylsilaneHCID 8058HexaneHCID 52153212,7-Dibromo-9,9-di-n-octylfluoreneHCID 178418339Butyllithium

Produkt 1

HCID 21932312(7-Bromo-9,9-dioctyl-9H-fluoren-2-yl)(trimethyl)silane

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

n-Butyllithium in hexane (6.0 mL, 1.6 M, 9.6 mmol) was added to a solution of 2,7-dibromo-9,9-di-n-octylfluorene (7) (5.00 g, 9.13 mmol) in dry THF (50 mL) in a schlenk flask at −78° C. and the mixture was stirred for 20 minutes. Then chlorotrimethylsilane (1.5 mL, 1.29 g, 1.3 equiv) was added and the reaction was allowed to slowly warm to room temperature. The mixture was stirred overnight and the reaction was quenched with saturated brine. The product was extracted into diethyl ether, and the extract was washed with brine and dried over MgSO4. The crude product was chromatographed on silica using hexane as eluent to give 2-bromo-7-trimethylsilyl-9,9-di-n-octylfluorene as a colourless oil, (3.50 g, 71%). n-Butyllithium in hexane (4.4 mL, 1.6 M, mmol) was added to a solution of 2-bromo-7-trimethylsilyl-9,9-di-n-octylfluorene (3.47 g, 6.41 mmol) in dry THF (75 mL) in a schlenk flask at −78° C., and the mixture was stirred for 20 minutes. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.44 mL, 1.31 g, 7.04 mmol) was added and the reaction was stirred for 24 h after warming to room temperature. The reaction was then quenched with brine, and the product was extracted into diethyl ether. The extract was washed with brine and dried over MgSO4. The crude product was chromatographed on silica using 0–3% ethylacetate in hexane as eluent, to give 8 as a colourless solid (2.67 g, 71%). 1H NMR (CD2Cl2): δ 7.73 (m, 4H) 7.51 (m, 2H) 1.99 (t, 4H, J=8.2 Hz) 1.36–0.54 (m, 42H) 0.31 (s, 9H)ppm. 13C NMR: δ 151.60, 151.34, 149.76, 145.29, 142.69, 141.07, 134.71, 133.01, 130.08, 129.03, 120.50, 120.25, 84.93, 56.22, 41.26, 33.01, 32.84, 31.11, 30.37, 25.98, 24.95, 23.85, 15.08, 0.01. FDMS m/z 588.90.

Aufarbeitung

  1. stirringThe mixture was stirred overnight
  2. customthe reaction was quenched with saturated brine
  3. extractionThe product was extracted into diethyl ether
  4. washthe extract was washed with brine
  5. dry with materialdried over MgSO4
  6. customThe crude product was chromatographed on silica

Quellen und Nachweise

ORD-Eintrag
ord-b4242553f71842e0b227dd193d15b429
Quelldatensatz
uspto-grants-2006_10
Patentnummer
US07115899B2

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