Ethyl Acetate → 2-({5-Chloro-2-[(1-ethyl-3-methyl-1H-pyrazol-5-yl)amino]-4-pyridinyl}amino)benzoic acid

HRID 62524

Reaktionsgleichung

Reaktionsgleichung von HRID 62524
[Cl:1][C:2]1[C:3]([NH:17][C:18]2C=[CH:24][CH:23]=[CH:22][C:19]=2C#N)=[CH:4][C:5]([NH:8][C:9]2[N:13]([CH2:14][CH3:15])[N:12]=[C:11]([CH3:16])[CH:10]=2)=[N:6][CH:7]=1.[OH-].[Na+].[C:28]([O:31]CC)(=[O:30])[CH3:29]>O1CCOCC1>[Cl:1][C:2]1[C:3]([NH:17][C:18]2[CH:19]=[CH:22][CH:23]=[CH:24][C:29]=2[C:28]([OH:31])=[O:30])=[CH:4][C:5]([NH:8][C:9]2[N:13]([CH2:14][CH3:15])[N:12]=[C:11]([CH3:16])[CH:10]=2)=[N:6][CH:7]=1

Komponenten

5

Edukt 3

HCID 8857Ethyl AcetateHCID 14798Sodium HydroxideHCID 593144512-({5-Chloro-2-[(1-ethyl-3-methyl-1H-pyrazol-5-yl)amino]-4-pyridinyl}amino)benzonitrile

Produkt 1

HCID 593144602-({5-Chloro-2-[(1-ethyl-3-methyl-1H-pyrazol-5-yl)amino]-4-pyridinyl}amino)benzoic acidAusbeute 66,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

To a 50 mL round bottom flask was added 2-({5-chloro-2-[(1-ethyl-3-methyl-1H-pyrazol-5-yl)amino]-4-pyridinyl}amino)benzonitrile (300 mg, 0.850 mmol), and NaOH 1 M solution (10 ml, 10.00 mmol) in 1,4-dioxane (10 mL). The mixture was heated under reflux for 18 hours. Ethyl acetate was added (20 mL) and the layers separated—all product stayed in the water phase. The water phase was neutralized with 6 N HCl, and 40 mL of ethyl acetate were added. The organic layer was separated, washed with brine, dried over MgSO4, filtered and evaporated. 2-({5-Chloro-2-[(1-ethyl-3-methyl-1H-pyrazol-5-yl)amino]-4-pyridinyl}amino)benzoic acid (220 mg, 0.562 mmol, 66.1% yield) was isolated as off-white solid and used in the next step without further purification. LCMS (M+H)+=372.1; 1H NMR (400 MHz, MeOD) ppm 1.33 (t, J=7.20 Hz, 4 H) 2.22 (s, 3 H) 4.00 (q, J=7.33 Hz, 2 H) 6.01 (s, 1 H) 6.82 (s, 1 H) 7.06 (td, J=7.52, 1.14 Hz, 1 H) 7.39-7.49 (m, 1 H) 7.49-7.55 (m, 1 H) 7.87-7.94 (m, 1 H) 8.05 (dd, J=7.83, 1.52 Hz, 1 H).

Aufarbeitung

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 18 hours
  3. customthe layers separated—all product
  4. additionwere added
  5. customThe organic layer was separated
  6. washwashed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-7395ac6ead584d759c88f6bfcdf97af7
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09446034B2

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