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 407414ノート

反応式

HRID 407414 の反応式
[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]

参加物

3

反応物 1

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
75 °C

実験手順

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, J1=8, J2=4, 1H), 6.63 (d, J=4, 1H), 3.72 (s, 3H), 3.70 (s, 3H).

後処理

  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)

出典と根拠

ORDレコード
ord-a95fdf98a3ce491a8cee0f420ce435b3
出典データセット
uspto-grants-2014_06
特許番号
US08754238B2

反応ノート

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