2,2'-Bithiophene → (6-[2,2']Bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilane

HRID 351301

Reaktionsgleichung

Reaktionsgleichung von HRID 351301
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[S:7][CH:8]=[CH:9][CH:10]=1.C([Li])CCC.Br[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25]>C1COCC1>[S:1]1[C:5]([CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][O:23][Si:24]([C:27]([CH3:28])([CH3:30])[CH3:29])([CH3:25])[CH3:26])=[CH:4][CH:3]=[C:2]1[C:6]1[S:7][CH:8]=[CH:9][CH:10]=1

Komponenten

5

Edukt 3

HCID 681202,2'-BithiopheneHCID 4260352(6-Bromohexyloxy)-tert-butyldimethylsilaneHCID 178418339Butyllithium

Produkt 1

HCID 58807316(6-[2,2']Bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilaneAusbeute 79,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a stirred solution of 2,2′-bithiophene (10.0 g, 60.24 mmol) in dry THF (150 ml) was added n-butyllithium (2.5 M in hexanes, 20.0 ml, 50.0 mmol) dropwise at −78° C. under nitrogen. After complete addition, the mixture was allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of 6-bromohexyloxy-tert-butyidimethylsilane (14.75 g, 50.0 mmol). The resultant mixture was stirred overnight at room temperature. The reaction was quenched with sat. aq. ammonium chloride, and the reaction mixture was extracted with ethyl acetate (3×70 ml). The combined organic extracts were washed with water, brine, and dried over magnesium sulphate. The solvent was removed under reduced pressure and the residue was purified by column chromatography (silica gel, petroleum/ethyl acetate from 100:0 to 20:1), to afford the product as a pale green oil (15.07 g, 79%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.08 (m, 1H, Ar—H), 7.03,(m, 1H, Ar—H), 6.92 (m, 2H, Ar—H), 6.61 (d, J=3.6 Hz, 1 H, Ar—H), 3.55 (t, J=6:2 Hz, 2H, OCH2), 3.34 (t, J=6.8 Hz, 2H, ArCH2), 1.25–1.85 (m, 8H, CH2), 0.86 (s, 9H, CH3), 0.01 (s, 6H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm).145.1 (quat.), 138.0 (quat.), 134.8 (quat.), 127.6 (CH), 124.7 (CH), 123.7 (CH), 123.4. (CH), 122.9 (CH), 63.0 (OCH2), 33.8 (CH2), 32.9 (CH2), 32.7 (CH2), 28.0 (CH2), 26.0 (CH3) 25.1 (CH2), 18.4 (quat.), −5.2 (CH3); MS (m/e): 380 (M+, 27%), 323 (63), 179 (100), 75 (37).

Aufarbeitung

  1. additionAfter complete addition
  2. customThe reaction was quenched with sat. aq. ammonium chloride
  3. extractionthe reaction mixture was extracted with ethyl acetate (3×70 ml)
  4. washThe combined organic extracts were washed with water, brine
  5. dry with materialdried over magnesium sulphate
  6. customThe solvent was removed under reduced pressure
  7. customthe residue was purified by column chromatography (silica gel, petroleum/ethyl acetate from 100:0 to 20:1)

Quellen und Nachweise

ORD-Eintrag
ord-a550147e60e546fab15368c3c0ed9a6d
Quelldatensatz
uspto-grants-2007_02
Patentnummer
US07183418B2

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