Aniline → HCID 70670709、化合物

HRID 1894978ノート

反応式

HRID 1894978 の反応式
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[CH:7][C:6]([C:12]([O:14][CH3:15])=[O:13])=[CH:5]2.[NH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C(=O)([O-])[O-].[Cs+].[Cs+].CN(C)C=O>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[C:17]1([NH:16][C:2]2[CH:3]=[C:4]3[C:9](=[CH:10][CH:11]=2)[N:8]=[CH:7][C:6]([C:12]([O:14][CH3:15])=[O:13])=[CH:5]3)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

参加物

7

反応物 4

HCID 6115AnilineHCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 53465709Methyl 6-bromoquinoline-3-carboxylate

生成物 1

HCID 70670709HCID 70670709、化合物

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒

反応条件

温度
100 °C

実験手順

Methyl 6-bromoquinoline-3-carboxylate (Int-1, 0.25 g, 0.94 mmol), aniline (94 μL, 1.0 mmol), palladium(II) acetate (21 mg, 0.094 mmol), 1,1′-binaphthalene-2,2′-diylbis(diphenylphosphine) (43 mg, 0.070 mmol), and cesium carbonate (431 mg, 1.32 mmol) were combined in a microwave vial fitted with a stirbar. N,N-Dimethylformamide (5.5 mL) was added, the vial was capped and the contents heated in a microwave at 100° C. for 1 h. The vial was cooled to room temperature, opened and the contents poured into water. The mixture was extracted three times with ethyl acetate. The extracts were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography (hexanes to 70/30 hexanes/ethyl acetate gradient) to afford pure Int-34. LC-MS: (FA) ES+ 279; 1H NMR (400 MHz, d6-DMSO) δ ppm 9.02 (d, J=2.1 Hz, 1 H), 8.79-8.74 (m, 2H), 7.94 (d, J=9.0 Hz, 1H), 7.67 (d, J=2.5 Hz, 1H), 7.62 (dd, J=9.1, 2.6 Hz, 1 H), 7.35-7.29 (m, 2H), 7.29-7.25 (m, 2H), 6.96 (tt, J=7.4, 7.4, 1.3, 1.3 Hz, 1H), 3.92 (s, 3H).

後処理

  1. customvial fitted with a stirbar
  2. customthe vial was capped
  3. temperatureThe vial was cooled to room temperature
  4. extractionThe mixture was extracted three times with ethyl acetate
  5. washThe extracts were washed with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe crude residue was purified by silica gel chromatography (hexanes to 70/30 hexanes/ethyl acetate gradient)
  10. customto afford pure Int-34

出典と根拠

ORDレコード
ord-49aa6f830a7a42d3861e5a344ae28019
出典データセット
uspto-grants-2013_08
特許番号
US08513421B2

反応ノート

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