Nitric Acid → 4-Methoxy-2-methyl-5-nitropyridine

HRID 509438ノート

反応式

HRID 509438 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][N:6]=[C:5]([CH3:9])[CH:4]=1.[N+:10]([O-])([OH:12])=[O:11].[OH-].[Na+]>OS(O)(=O)=O>[CH3:1][O:2][C:3]1[C:8]([N+:10]([O-:12])=[O:11])=[CH:7][N:6]=[C:5]([CH3:9])[CH:4]=1

参加物

5

反応物 3

HCID 944Nitric AcidHCID 14798Sodium HydroxideHCID 47377584-Methoxy-2-methylpyridine

生成物 1

HCID 735537124-Methoxy-2-methyl-5-nitropyridine

試薬・触媒・溶媒 1

HCID 1118Sulfuric Acid溶媒2 回

反応条件

温度
65 °C

実験手順

To a stirred solution of 4-methoxy-2-methylpyridine (25 g, 0.148 mol) in conc. H2SO4 (17 mL, S. D. Fine, India), a mixture of H2SO4 (17 mL, S.D. Fine, India) and 65% HNO3 (22 mL, Rankem, India) was added in a drop-wise fashion at 0° C. over 30 min. The resulting solution was heated at 65° C. for 12 h. After completion, the reaction mixture was poured in to ice water and neutralized (PH-8) with 40% NaOH solution to give a yellow precipitate. The precipitate was further stirred and filtered, dried to give a mixture of 3-nitro (major product) and the desired 5-nitro isomers. The product was isolated by column chromatography, silica gel (230-400), eluting with 15% EtOAc in petroleum ether to give the title compound as yellow needles. 1H NMR (400 MHz, DMSO-d6) δ: 8.86 (s, 1H), 7.33 (s, 1H), 3.99 (s, 3H), 2.52 (s, 3H). MS (ESI, positive ion) m/z: 169.0 (M+H).

後処理

  1. additionwas added in a drop-wise fashion at 0° C. over 30 min
  2. customto give a yellow precipitate
  3. filtrationfiltered
  4. customdried
  5. customto give
  6. additiona mixture of 3-nitro (major product)
  7. customThe product was isolated by column chromatography, silica gel (230-400)
  8. washeluting with 15% EtOAc in petroleum ether

出典と根拠

ORDレコード
ord-bfe56e48939f44188a075c9826c8cb09
出典データセット
uspto-grants-2015_08
特許番号
US09096527B2

反応ノート

読み込み中…