Hydrochloric Acid → 3-Chloroisoquinoline

HRID 40664

反応式

HRID 40664 の反応式
N[C:2]1[N:3]=[CH:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[CH:7][CH:6]=2.N([O-])=O.[Na+].C([O-])(O)=O.[Na+].[ClH:21]>>[Cl:21][C:2]1[N:3]=[CH:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[CH:7][CH:6]=2

参加物

5

反応物 4

HCID 313Hydrochloric AcidHCID 311869Isoquinolin-3-AmineHCID 516892Sodium BicarbonateHCID 23668193Sodium Nitrite

生成物 1

HCID 6409683-Chloroisoquinoline収率 51%

反応条件

温度
0 °C

実験手順

3-Aminoisoquinoline (1.44 g, 10 mmol) was suspended in 10M HCl (5 mL) and cooled to 0° C. Sodium nitrite (689 mg, 10 mmol) was added in portions over 5 minutes. The reaction mixture was stirred at 0° C. for 2 hours and allowed to warm to room temperature over 1 hour. The reaction mixture was added carefully to saturated NaHCO3 solution (200 mL) and extracted into ethyl acetate. The insoluble byproduct was removed by filtration and the aqueous layer was re-extracted into ethyl acetate. The combined organics were washed with water and brine, dried (Na2SO4) and concentrated to a brown oil which solidified on standing. Flash chromatography on silica, eluting with dichloromethane, gave the title compound as a white solid (827 mg, 5.05 mmol, 51%). 1H NMR (d6-DMSO, 400 MHz) δ 9.12 (s, 1H), 8.41 (s, 1H), 8.12 (dd, 1H, J=7.5, 1.0 Hz), 7.93-7.90 (m, 1H), 7.84-7.80 (m, 1H), 7.74-7.70 (m, 1H). LCMS (1) Rt=1.79 min; m/z (ESI+) 164 (MH+).

後処理

  1. temperatureto warm to room temperature over 1 hour
  2. extractionextracted into ethyl acetate
  3. customThe insoluble byproduct was removed by filtration
  4. extractionthe aqueous layer was re-extracted into ethyl acetate
  5. washThe combined organics were washed with water and brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated to a brown oil which
  8. washFlash chromatography on silica, eluting with dichloromethane

出典と根拠

ORDレコード
ord-dd66e5c0180f4da9ab248d1974c98047
出典データセット
uspto-grants-2013_09
特許番号
US08530468B2

関連ノート

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