4-Chloro-5-(2-methoxy-5-nitro-phenyl)-1-methyl-1H-pyrazole → 3-(4-Chloro-2-methyl-2H-pyrazol-3-yl)4-methoxy-phenylamine

HRID 540529노트

반응식

HRID 540529 반응식
[Cl:1][C:2]1[CH:3]=[N:4][N:5]([CH3:18])[C:6]=1[C:7]1[CH:12]=[C:11]([N+:13]([O-])=O)[CH:10]=[CH:9][C:8]=1[O:16][CH3:17]>CCO>[Cl:1][C:2]1[CH:3]=[N:4][N:5]([CH3:18])[C:6]=1[C:7]1[CH:12]=[C:11]([NH2:13])[CH:10]=[CH:9][C:8]=1[O:16][CH3:17]

참가 물질

3

반응물 1

HCID 231395374-Chloro-5-(2-methoxy-5-nitro-phenyl)-1-methyl-1H-pyrazole

생성물 1

HCID 231395183-(4-Chloro-2-methyl-2H-pyrazol-3-yl)4-methoxy-phenylamine수율 86%

시약·촉매·용매 1

HCID 702Ethanol용매

반응 조건

온도
75 °C

실험 절차

4-Chloro-5-(2-methoxy-5-nitro-phenyl)-1-methyl-1H-pyrazole (2.27 g, 8.5 mmol) was dissolved in dry EtOH (150 mL) and heated to 75° C. The heated solution was then treated with Sn(II) chloride dihydrate (9.6 g, 42.5 mmol) and stirred at 75° C. After three hours, the reaction was found to be complete by TLC and LCMS. The solvent was removed under reduced pressure. The residue was subsequently diluted with EtOAc (100 mL) and 1N NaOH, neutralizing the reaction to a pH of approximately 6 or 7. The mix was then filtered through celite. The organic layer was separated, and the aqueous layer was extracted with EtOAc (2×50 mL). The organic layers were combined, dried over Na2SO4, filtered, and the solvent removed under reduced pressure. The residue was then purified by flash chromatography (Biotage, SiO2, Hexanes/EtOAc gradient elution) to afford 1.73 g (86%) of 3-(4-chloro-2-methyl-2H-pyrazol-3-yl)-4-methoxy-phenylamine as a light brown solid. LCMS m/z (%) 240 (M+H37Cl, 37), 238 (M+H35Cl, 100). 1H NMR (400 MHz, CDCl3) δ: 7.48 (s, 1H), 6.87 (d, J=8, 1H), 6.81 (dd, j=8, J=4, 1H), 6.63 (d, J=4, 1H), 3.72 (s, 3H), 3.70 (s, 3H).

후처리

  1. customThe solvent was removed under reduced pressure
  2. additionThe residue was subsequently diluted with EtOAc (100 mL) and 1N NaOH
  3. customthe reaction to a pH of approximately 6 or 7
  4. filtrationThe mix was then filtered through celite
  5. customThe organic layer was separated
  6. extractionthe aqueous layer was extracted with EtOAc (2×50 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. customthe solvent removed under reduced pressure
  10. customThe residue was then purified by flash chromatography (Biotage, SiO2, Hexanes/EtOAc gradient elution)

출처 및 근거

ORD 기록
ord-327ffbc90ccb4eb79a3b02c076079c2a
출처 데이터셋
uspto-grants-2014_10
특허 번호
US08871797B2

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