Thieno(3,2-b)thiophene → HCID 58991632、化合物

HRID 644118ノート

反応式

HRID 644118 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

HCID 58991632HCID 58991632、化合物収率 77%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-1008bac230b54a058c0fceb26b927eaa
出典データセット
uspto-grants-2010_04
特許番号
US07700643B2

反応ノート

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