Thieno(3,2-b)thiophene → HCID 58991632, Verbindung

HRID 644118Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 644118
[S:1]1[CH:5]=[CH:4][C:3]2[S:6][CH:7]=[CH:8][C:2]1=2.C([Li])CCC.Br[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][O:21][CH2:22][C:23]1([CH2:27][CH3:28])[CH2:26][O:25][CH2:24]1>C1COCC1>[CH2:27]([C:23]1([CH2:22][O:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][C:5]2[S:1][C:2]3[CH:8]=[CH:7][S:6][C:3]=3[CH:4]=2)[CH2:24][O:25][CH2:26]1)[CH3:28]

Komponenten

5

Edukt 3

HCID 136063Thieno(3,2-b)thiopheneHCID 592073103-{[(6-Bromohexyl)oxy]methyl}-3-ethyloxetaneHCID 178418339Butyllithium

Produkt 1

HCID 58991632HCID 58991632, VerbindungAusbeute 77 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a stirred solution of thieno(3,2-b)thiophene (5.0 g, 35.7 mmol) in anhydrous THF (120 ml) was added n-butyllithium (2.5 M in hexanes, 12.0 ml, 30.0 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 3-(6-bromohexyloxymethyl)-3-ethyloxetane (8.38 g, 30.0 mmol). The resultant mixture was stirred overnight at room temperature. The reaction was quenched with sat. aq. NH4Cl, 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 on silica, eluting with petroleum ether/ethyl acetate (9:1), to give a yellow oil (7.82 g, 77%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.22 (d, J=5.3 Hz, 1H, Ar—H), 7.14 (d, J=5.3 Hz, 1H, Ar—H), 6.91 (s, 1H, Ar—H), 4.43 (d, J=5.8 Hz, 2H, OCH2), 4.35 (d, J=5.8 Hz, 2H, OCH2), 3.48 (s, 2H, OCH2), 3.41 (t, J=6.4 Hz, 2H, OCH2), 2.84 (t, J=7.4 Hz 2H, ArCH2), 1.35-1.75 (m, 10H, CH2), 0.86 (t, J=7.6 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 148.3 (quat.), 138.8 (quat.), 137.4 (quat.), 125.4 (CH), 119.5 (CH), 116.3 (CH), 78.6 (OCH2), 73.4 (OCH2), 71.5 (OCH2), 43.4 (quat.), 31.6 (CH2), 31.2 (CH2), 29.5 (CH2), 28.9 (CH2) 26.8 (CH2), 26.0 (CH2), 8.3 (CH3); MS (m/e): 490 (M+, 16%) □305 (79), 223 (25), 205 (100).

Aufarbeitung

  1. additionAfter complete addition
  2. customThe reaction was quenched with sat. aq. NH4Cl
  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 on silica
  8. washeluting with petroleum ether/ethyl acetate (9:1)

Quellen und Nachweise

ORD-Eintrag
ord-1008bac230b54a058c0fceb26b927eaa
Quelldatensatz
uspto-grants-2010_04
Patentnummer
US07700643B2

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