Methyl 4-cyano-2-methyl-5-nitrobenzoate → Methyl 5-amino-4-cyano-2-methylbenzoate

HRID 906152ノート

反応式

HRID 906152 の反応式
[C:1]([C:3]1[C:12]([N+:13]([O-])=O)=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:16])[CH:4]=1)#[N:2]>C(O)(=O)C.[Fe]>[NH2:13][C:12]1[C:3]([C:1]#[N:2])=[CH:4][C:5]([CH3:16])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

参加物

4

反応物 1

HCID 67403131Methyl 4-cyano-2-methyl-5-nitrobenzoate

生成物 1

HCID 67402842Methyl 5-amino-4-cyano-2-methylbenzoate収率 91.5%

試薬・触媒・溶媒 2

HCID 23925Iron触媒HCID 176Acetic Acid溶媒

反応条件

温度
45 °C

実験手順

To a solution of methyl 4-cyano-2-methyl-5-nitrobenzoate (14.8 g, 0.0672 mol) in acetic acid (250 mL) was added iron powder (22.5 g, 0.40 mol). The reaction mixture was heated to 45° C. and stirred for 1 h, at which time it was cooled to room temperature. The reaction mixture was filtered through a bed of celite, and the filter cake rinsed with ethyl acetate. The volume of the filtrate was reduced by half and then partitioned between water and ethyl acetate. The organic layer was washed with 10% lithium chloride followed by saturated aqueous sodium bicarbonate. The organic layer was further washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was triturated with hexanes to afford methyl 5-amino-4-cyano-2-methylbenzoate (11.7 g, 91%) as a bright yellow powder. 1H NMR (400 MHz, CDCl3): 7.28 (s, 1H), 7.26 (s, 1H), 4.35 (br s, 2H), 3.89 (s, 3H), 2.43 (s, 3H). MS (EI) for C10H10N2O2: 191 (MH+).

後処理

  1. temperaturewas cooled to room temperature
  2. filtrationThe reaction mixture was filtered through a bed of celite
  3. washthe filter cake rinsed with ethyl acetate
  4. custompartitioned between water and ethyl acetate
  5. washThe organic layer was washed with 10% lithium chloride
  6. washThe organic layer was further washed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residue was triturated with hexanes

出典と根拠

ORDレコード
ord-8af1536ff29d4759b1bcd98611888295
出典データセット
uspto-grants-2011_09
特許番号
US08012956B2

反応ノート

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