Acetic Acid → Methyl 2-(4-amino-3-bromophenyl)acetate

HRID 350446ノート

反応式

HRID 350446 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([CH2:11][C:12]([O:14][CH3:15])=[O:13])[CH:5]=[CH:6][C:7]=1[N+:8]([O-])=O.C(O[Na])(C)=O.O.O.O.CC(O)=O>CO.O>[NH2:8][C:7]1[CH:6]=[CH:5][C:4]([CH2:11][C:12]([O:14][CH3:15])=[O:13])=[CH:3][C:2]=1[Br:1]

参加物

5

反応物 3

HCID 176Acetic AcidHCID 23512304Methyl (3-bromo-4-nitrophenyl)acetateHCID 178476686sodium;acetate;trihydrate

生成物 1

HCID 15462911Methyl 2-(4-amino-3-bromophenyl)acetate収率 69%

試薬・触媒・溶媒 1

HCID 22242641Methanol--water (1/1)溶媒

反応条件

温度
90 °C

実験手順

A mixture of methyl 3-bromo-4-nitrophenylacetate (14.8 g, 53.8 mmol), reduced iron powder (9.62 g, 172 mmol), AcONa.3H2O (7.32 g, 53.8 mmol) and AcOH (20.0 ml) in MeOH/H2O (150/600 ml) was heated at 90° C. for 1 h. After cooled to room temperature, the reaction mixture was filtered through Celite and the filtered cake was washed with MeOH. The combined filtrate were evaporated and extracted with EtOAc. The extracts were washed with brine, dried over Na2SO4 and concentrated in vacuo. The residue was chromatographed on silica gel [400 g, CHCl3/EtOAc (20/1)] to give methyl 4-amino-3-bromophenylacetate (9.01 g, 69%) as a brown oil. 1H-NMR (CDCl3) δ 3.48 (s, 2H), 3.68 (s, 3H), 4.05 (br, 2H), 6.69 (d, J=8.3 Hz, 1H), 7.00 (dd, J=8.1, 2.0 Hz, 1H), 7.32 (d, J=2.0 Hz, 1H).

後処理

  1. temperatureAfter cooled to room temperature
  2. filtrationthe reaction mixture was filtered through Celite
  3. washthe filtered cake was washed with MeOH
  4. customThe combined filtrate were evaporated
  5. extractionextracted with EtOAc
  6. washThe extracts were washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated in vacuo
  9. customThe residue was chromatographed on silica gel [400 g, CHCl3/EtOAc (20/1)]

出典と根拠

ORDレコード
ord-34b91b524ede4458baa24574c7e61c92
出典データセット
uspto-grants-2007_02
特許番号
US07179819B2

反応ノート

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