Stannous chloride dihydrate → 5-Bromo-2-fluoro-4-methylaniline

HRID 39196

反応式

HRID 39196 の反応式
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[C:5]([F:11])=[CH:4][C:3]=1[CH3:12].O.O.Cl[Sn]Cl.C([O-])(O)=O.[Na+]>C(O)C>[Br:1][C:2]1[C:3]([CH3:12])=[CH:4][C:5]([F:11])=[C:6]([CH:7]=1)[NH2:8]

参加物

5

反応物 3

HCID 61436Stannous chloride dihydrateHCID 516892Sodium BicarbonateHCID 100369831-Bromo-4-fluoro-2-methyl-5-nitrobenzene

生成物 1

HCID 467391145-Bromo-2-fluoro-4-methylaniline収率 31.9%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

To a stirred solution of 1-bromo-4-fluoro-2-methyl-5-nitrobenzene (18.0 g) in ethanol (300 mL) was added SnCl2.2H2O (51.8 g, 0.230 mol) at room temperature. The mixture was heated at reflux for 3 h. The solvent was evaporated under reduced pressure to give a residue, which was poured into ice water. The aqueous phase was basified with sat. NaHCO3 to pH 7. The solid was filtered off and the filtrate was extracted with dichloromethane (200 mL×3). The combined organics were dried over anhydrous Na2SO4 and evaporated under reduced pressure. The residue was purified by column chromatography (petroleum ether/EtOAc=10/1) to afford 5-bromo-2-fluoro-4-methylaniline (5.0 g, 30% yield for two steps). 1NMR (400 MHz, CDCl3) δ 6.96 (d, J=8.8 Hz, 1H), 6.86 (d, J=11.6 Hz, 1H), 3.64 (br, 2H), 2.26 (s, 3H). MS (ESI) m/z (M+H+) 204.0.

後処理

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 3 h
  3. customThe solvent was evaporated under reduced pressure
  4. customto give a residue, which
  5. filtrationThe solid was filtered off
  6. extractionthe filtrate was extracted with dichloromethane (200 mL×3)
  7. dry with materialThe combined organics were dried over anhydrous Na2SO4
  8. customevaporated under reduced pressure
  9. customThe residue was purified by column chromatography (petroleum ether/EtOAc=10/1)

出典と根拠

ORDレコード
ord-4faec5fa3e7a4b489140c41b8b82cf54
出典データセット
uspto-grants-2013_09
特許番号
US08524767B2

関連ノート

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