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

HRID 589103Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 589103
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

Komponenten

8

Edukt 3

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

Produkt 1

HCID 904099173-(2-Bromopyridin-3-yl)-5-nitro-3,4-dihydro-2H-1,4-benzoxazin-3-olAusbeute 90,2 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

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.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-a8b08553725640e6aadc839e1a075c85
Quelldatensatz
uspto-grants-2016_01
Patentnummer
US09227985B2

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