Methane → 3-Nitro-(quinoxalinylamino)benzoic acid

HRID 1267000

反応式

HRID 1267000 の反応式
N[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[N:4]=[CH:5][CH:6]=[N:7]2.Br[C:13]1[C:21]([N+:22]([O-:24])=[O:23])=[CH:20][CH:19]=[CH:18][C:14]=1[C:15]([OH:17])=[O:16].C([N:27]1CCOCC1)C.C>C(O)(C)C.N>[N+:22]([C:21]1[C:13]([NH:27][C:6]2[CH:5]=[N:4][C:3]3[C:8](=[CH:9][CH:10]=[CH:11][CH:2]=3)[N:7]=2)=[C:14]([CH:18]=[CH:19][CH:20]=1)[C:15]([OH:17])=[O:16])([O-:24])=[O:23]

参加物

7

反応物 4

HCID 297MethaneHCID 7525EthylmorpholineHCID 684522-Bromo-3-nitrobenzoic acidHCID 854945-Aminoquinoxaline

生成物 1

HCID 185454443-Nitro-(quinoxalinylamino)benzoic acid収率 42%

試薬・触媒・溶媒 2

HCID 222Ammonia溶媒HCID 3776Isopropanol溶媒

反応条件

温度
67.5 °C

実験手順

A mixture of 5-aminoquinoxaline (1.0 g, 6.89 mmol), 2-bromo-3-nitrobenzoic acid (4.0 g, 13.78 mmol), Cu/CuI (catalytic) and N-ethylmorpholine (5 mL) in isopropanol (5 mL) was heated at 65-70° C. overnight. The mixture was then dissolved in aqueous ammonia, treated with charcoal/Celite, and filtered. The filtrate was acidified with conc. HCl, and the resulting precipitate was collected while the mixture was still warm and washed with water (to remove unreacted 2-bromo-3-nitrobenzoic acid). It was then dried and chromatographed on silica gel, eluting with CH2Cl2/MeOH (19:1), to give 3-nitro-(quinoxalinylamino)benzoic acid (0.9 g, 42%): mp (MeOH) 232-237° C.; 1H NMR [(CD3)2SO] δ 6.92-6.97 (m, 1 H, ArH), 7.30 (t, J=8.0 Hz, 1 H, ArH), 7.62-7.66 (m, 2 H, 2xArH), 8.23 (dd, J=8.2, 1.6 Hz, 1 H, ArH), 8.29 (dd, J=7.8, 1.6 Hz, 1 H, ArH), 8.97 (d, J=1.7 Hz, 1 H, H-2′ or H-3′), 9.03 (d, J=1.9 Hz, 1 H, H-2′ or H-3′), 10.73 (br s, 1 H, NH), 13.8 (br s, 1 H, CO2H).

後処理

  1. filtrationfiltered
  2. customthe resulting precipitate was collected while the mixture
  3. temperaturewas still warm
  4. washwashed with water (to remove unreacted 2-bromo-3-nitrobenzoic acid)
  5. customIt was then dried
  6. customchromatographed on silica gel
  7. washeluting with CH2Cl2/MeOH (19:1)

出典と根拠

ORDレコード
ord-86d5a59d56cc4c9c93605e5cfd06affe
出典データセット
uspto-grants-2003_04
特許番号
US06552021B2

関連ノート

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