Potassium Carbonate → 3-(2-Bromopyridin-3-yl)-5-nitro-3,4-dihydro-2H-1,4-benzoxazin-3-ol

HRID 589103노트

반응식

HRID 589103 반응식
Br[CH2:2][C:3]([C:5]1[C:6]([Br:11])=[N:7][CH:8]=[CH:9][CH:10]=1)=[O:4].C(=O)([O-])[O-].[K+].[K+].[NH2:18][C:19]1[C:24]([N+:25]([O-:27])=[O:26])=[CH:23][CH:22]=[CH:21][C:20]=1[OH:28]>C(Cl)Cl.O.CCCC[N+](CCCC)(CCCC)CCCC.[Br-].[Cl-].[Na+].O>[Br:11][C:6]1[C:5]([C:3]2([OH:4])[NH:18][C:19]3[C:24]([N+:25]([O-:27])=[O:26])=[CH:23][CH:22]=[CH:21][C:20]=3[O:28][CH2:2]2)=[CH:10][CH:9]=[CH:8][N:7]=1

참가 물질

8

반응물 3

HCID 11430Potassium CarbonateHCID 41154952-Amino-3-NitrophenolHCID 534166012-Bromo-1-(2-bromopyridin-3-YL)ethanone

생성물 1

HCID 904099173-(2-Bromopyridin-3-yl)-5-nitro-3,4-dihydro-2H-1,4-benzoxazin-3-ol수율 90.2%

시약·촉매·용매 4

HCID 74236Tetrabutylammonium Bromide촉매HCID 962Water용매HCID 6344Dichloromethane용매HCID 57417360Sodium chloride; water용매

반응 조건

온도
40 °C

실험 절차

A solution of 2-bromo-1-(2-bromopyridin-3-yl)ethanone (2.15 g, 7.71 mmol) in methylene chloride (77.1 mL) and water (19.3 mL) was treated with potassium carbonate (2.13 g, 15.4 mmol), tetra-N-butylammonium bromide (500 mg, 1.50 mmol), and 2-amino-3-nitrophenol (1.31 g, 8.48 mmol), and heated at 40° C. for 5 h. The reaction mixture was then diluted with brine. The aqueous layer was separated and extracted with dichloromethane (2×100 mL). The combined organic layers were washed with water and brine, dried over magnesium sulfate, filtered, and concentrated to give the crude product. Purification by flash column chromatography (100% hexanes to 35% ethyl acetate/hexanes) gave the desired product (2.45 g, 90%) as a racemic mixture. LCMS calculated for C13H11BrN3O4 (M+H)+: m/z=352.0, 354.0. found: 351.7, 353.8.

후처리

  1. customThe aqueous layer was separated
  2. extractionextracted with dichloromethane (2×100 mL)
  3. washThe combined organic layers were washed with water and brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give the crude product
  8. customPurification by flash column chromatography (100% hexanes to 35% ethyl acetate/hexanes)

출처 및 근거

ORD 기록
ord-a8b08553725640e6aadc839e1a075c85
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09227985B2

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