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

HRID 644118노트

반응식

HRID 644118 반응식
[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]

참가 물질

5

반응물 3

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

생성물 1

HCID 58991632HCID 58991632, 화합물수율 77%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-1008bac230b54a058c0fceb26b927eaa
출처 데이터셋
uspto-grants-2010_04
특허 번호
US07700643B2

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