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

HRID 906152노트

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HRID 906152 반응식
[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]

참가 물질

4

반응물 1

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

생성물 1

HCID 67402842Methyl 5-amino-4-cyano-2-methylbenzoate수율 91.5%

시약·촉매·용매 2

HCID 23925Iron촉매HCID 176Acetic Acid용매

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온도
45 °C

실험 절차

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+).

후처리

  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

출처 및 근거

ORD 기록
ord-8af1536ff29d4759b1bcd98611888295
출처 데이터셋
uspto-grants-2011_09
특허 번호
US08012956B2

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