Thionyl Chloride → 3-(6-hydroxy-1,3-benzodioxol-5-yl)-1-pentyl-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one

HRID 1715209노트

반응식

HRID 1715209 반응식
O[C:2]1([C:17]2[C:25]([OH:26])=[CH:24][C:20]3[O:21][CH2:22][O:23][C:19]=3[CH:18]=2)[C:10]2[C:5](=[N:6][CH:7]=[CH:8][CH:9]=2)[N:4]([CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])[C:3]1=[O:16].C(N(C(C)C)CC)(C)C.S(Cl)(Cl)=O>ClCCl.[Zn]>[OH:26][C:25]1[C:17]([CH:2]2[C:10]3[C:5](=[N:6][CH:7]=[CH:8][CH:9]=3)[N:4]([CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])[C:3]2=[O:16])=[CH:18][C:19]2[O:23][CH2:22][O:21][C:20]=2[CH:24]=1

참가 물질

6

반응물 3

HCID 24386Thionyl ChlorideHCID 81531DiisopropylethylamineHCID 119627703-hydroxy-3-(6-hydroxy-1,3-benzodioxol-5-yl)-1-pentyl-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one

생성물 1

HCID 119627743-(6-hydroxy-1,3-benzodioxol-5-yl)-1-pentyl-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one수율 76.6%

시약·촉매·용매 2

HCID 23994Zinc촉매HCID 6344Dichloromethane용매

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온도
0 °C

실험 절차

To a solution of 3-hydroxy-3-(6-hydroxy-1,3-benzodioxol-5-yl)-1-pentyl-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one (4.00 g, 11.2 mmol) in anhydrous dichloromethane (80.0 mL) was added diisopropylethylamine (6.10 mL) and thionyl chloride (2.77 g, 23.5 mmol) under nitrogen at 0° C. The reaction mixture was stirred at 0° C. for 1 h and concentrated in vacuo to dryness. The residue was dissolved in THF/acetic acid (7:3, 100 mL) followed by the addition of Zn dust (3.08 g, 47.1 mmol) in one portion. The reaction mixture was stirred at ambient temperature for 16 h, filtered and the residue was washed with ethyl acetate (30.0 mL). The filtrate was concentrated in vacuo to dryness. The residue was dissolved in ethyl acetate (200 mL), washed with saturated ammonium chloride (3×50.0 mL), dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to dryness. The residue was subjected to column chromatography to give the title compound (2.92 g, 76%): 1H NMR (300 MHz, CDCl3) δ 8.64 (br, 1H), 8.26 (d, 1H), 7.52 (d, 1H), 7.05 (dd, 1H), 6.53 (s, 1H), 6.25 (s, 1H), 5.84 (d, 2H), 5.02 (s, 1H), 3.86-3.75 (m, 2H), 1.76-1.67 (m, 2H), 1.33-1.28 (m, 4H), 0.85 (t, 3H); 13C NMR (75 MHz, CDCl3) δ 178.5, 157.4, 150.9, 147.8, 147.5, 141.6, 133.2, 121.7, 118.7, 114.1, 106.4, 101.2, 101.1, 46.5, 39.8, 28.9, 27.3, 22.3, 13.9; MS (ES+) m/z 341 (M+1).

후처리

  1. concentrationconcentrated in vacuo to dryness
  2. dissolutionThe residue was dissolved in THF/acetic acid (7:3, 100 mL)
  3. stirringThe reaction mixture was stirred at ambient temperature for 16 h
  4. filtrationfiltered
  5. washthe residue was washed with ethyl acetate (30.0 mL)
  6. concentrationThe filtrate was concentrated in vacuo to dryness
  7. dissolutionThe residue was dissolved in ethyl acetate (200 mL)
  8. washwashed with saturated ammonium chloride (3×50.0 mL)
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated in vacuo to dryness

출처 및 근거

ORD 기록
ord-1aa4e17771824102a7ebde8bd7563b09
출처 데이터셋
uspto-grants-2010_09
특허 번호
US07799798B2

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