Ethyl formate → 6,7-Dimethoxy-4-hydroxyquinoline

HRID 15507

反応式

HRID 15507 の反応式
[NH2:1][C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([O:10][CH3:11])=[CH:4][C:3]=1[C:12](=[O:14])[CH3:13].C[O-].[Na+].[CH:18](OCC)=O.CCOC(C)=O>COCCOC.O>[CH3:11][O:10][C:5]1[CH:4]=[C:3]2[C:2](=[CH:7][C:6]=1[O:8][CH3:9])[NH:1][CH:18]=[CH:13][C:12]2=[O:14]

参加物

7

反応物 4

HCID 8025Ethyl formateHCID 8857Ethyl AcetateHCID 602085Ethanone, 1-(2-amino-4,5-dimethoxyphenyl)-HCID 10942334Sodium Methoxide

生成物 1

HCID 4596116,7-Dimethoxy-4-hydroxyquinoline収率 95%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 80711,2-Dimethoxyethane溶媒

実験手順

To a solution of 1-(2-amino-4,5-dimethoxyphenyl)ethanone (9.80 g, 50 mmol, Lancaster Synthesis LTD) in DME (300 mL) at rt was added NaOMe (15.0 g, 278 mmol), and the mixture was stirred for 30 minutes at rt. To this mixture was added ethyl formate (25 mL) dropwise with stirring at rt. After an hour the reaction was quenched by adding aq HCl (50 mL of 2N HCl), stirred for 10 minutes and the precipitate was filtered, washed with a small amount of H2O and EtOAc to obtain the 1st crop of product. To the filtrate solution was added EtOAc (200 mL), the EtOAc layer was separated, the aqueous layer was washed with EtOAc (200 mL), and the combined EtOAc solution was dried over MgSO4, concentrated in vacuo and the residue was triturated with a small amount of CH3OH/EtOAc to obtain the 2nd crop of product. The solids of 1st crop and 2nd crop were combined, mixed with water (100 mL), stirred for 10 minutes, the solid was filtered and dried to obtain the product (9.75 g, 95%) as a white solid. 1H NMR (DMSO-d6) δ 8.50 (s, 1H), 7.75 (d, 1H, J=4.2 Hz), 7.42 (s, 1H), 7.08 (s, 1H), 5.91 (d, 1H, J=4.2 Hz), 3.83 (s, 3H), 3.80 (s, 3H).

後処理

  1. stirringwith stirring at rt
  2. customAfter an hour the reaction was quenched
  3. additionby adding aq HCl (50 mL of 2N HCl)
  4. stirringstirred for 10 minutes
  5. filtrationthe precipitate was filtered
  6. washwashed with a small amount of H2O and EtOAc
  7. customto obtain the 1st crop of product
  8. customthe EtOAc layer was separated
  9. washthe aqueous layer was washed with EtOAc (200 mL)
  10. dry with materialthe combined EtOAc solution was dried over MgSO4
  11. concentrationconcentrated in vacuo
  12. customthe residue was triturated with a small amount of CH3OH/EtOAc
  13. customto obtain the 2nd crop of product
  14. stirringstirred for 10 minutes
  15. filtrationthe solid was filtered
  16. customdried

出典と根拠

ORDレコード
ord-a0b786fdb5d448f4bc11f885845c25b7
出典データセット
uspto-grants-2010_06
特許番号
US07732613B2

関連ノート

読み込み中…