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 540529Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 540529
[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]

Komponenten

3

Edukt 1

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Reaktionsbedingungen

Temperatur
75 °C

Versuchsvorschrift

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).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-327ffbc90ccb4eb79a3b02c076079c2a
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08871797B2

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