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

HRID 589103ノート

反応式

HRID 589103 の反応式
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

参加物

8

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 4

HCID 74236Tetrabutylammonium Bromide触媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 57417360Sodium chloride; water溶媒

反応条件

温度
40 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-a8b08553725640e6aadc839e1a075c85
出典データセット
uspto-grants-2016_01
特許番号
US09227985B2

反応ノート

読み込み中…