Ethyl 2-pyridinecarboxylate → 1-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)-3-(pyridin-2-yl)propane-1,3-dione

HRID 623798노트

반응식

HRID 623798 반응식
[O:1]1[CH2:6][CH2:5][O:4][C:3]2[CH:7]=[C:8]([C:11](=[O:13])[CH3:12])[CH:9]=[CH:10][C:2]1=2.[H-].[Na+].[N:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[C:22](OCC)=[O:23]>C1COCC1>[O:1]1[CH2:6][CH2:5][O:4][C:3]2[CH:7]=[C:8]([C:11](=[O:13])[CH2:12][C:22]([C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][N:16]=3)=[O:23])[CH:9]=[CH:10][C:2]1=2

참가 물질

5

반응물 3

HCID 17307Ethyl 2-pyridinecarboxylateHCID 24758Sodium hydrideHCID 761431,4-Benzodioxan-6-yl methyl ketone

생성물 1

HCID 568403841-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)-3-(pyridin-2-yl)propane-1,3-dione수율 71%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

A solution of 1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)ethanone (XV) (1 eq) in THF was added slowly to a suspension of NaH (1.5 eq) in THF stirred under nitrogen at room temperature. The solution was further allowed to stir at room temperature until the evolution of gas was ceased. Ethyl picolinate (XIX) (1.1 eq) was added to the solution and refluxed overnight under nitrogen. The solution was cooled, poured into ice water and extracted with ethyl acetate. The organic layer was dried over MgSO4, filtered and concentrated under vacuum. The crude product was purified by column chromatography over silica gel to produce 1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-3-(pyridin-2-yl)propane-1,3-dione 15 as a yellow solid (71% yield), 1H NMR (CDCl3, 400 MHz): δ ppm 4.13-4.43 (m, 4H), 6.94 (d, J=8.31 Hz, 1H), 7.42 (m, 1H), 7.44 (m, 1H) 7.59 (m, 2H), 7.85 (m, 1H), 8.14 (d, J=7.81, 1H), 8.65 (m, 1H); ESIMS found C16H13NO4 m/z 284 (M+H).

후처리

  1. stirringto stir at room temperature until the evolution of gas
  2. temperaturerefluxed overnight under nitrogen
  3. temperatureThe solution was cooled
  4. extractionextracted with ethyl acetate
  5. dry with materialThe organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe crude product was purified by column chromatography over silica gel

출처 및 근거

ORD 기록
ord-b5a6a2f1403344c59bdc7007e019a46a
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09303010B2

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