Hydrochloric Acid → Ethyl 5-Chloro-1-methyl-1H-pyrazole-4-carboxylate

HRID 12823

Reaktionsgleichung

Reaktionsgleichung von HRID 12823
N(OC(C)(C)C)=O.[CH2:8]([O:10][C:11]([C:13]1[CH:14]=[N:15][N:16]([CH3:19])[C:17]=1N)=[O:12])[CH3:9].[ClH:20]>C(#N)C>[CH2:8]([O:10][C:11]([C:13]1[CH:14]=[N:15][N:16]([CH3:19])[C:17]=1[Cl:20])=[O:12])[CH3:9]

Komponenten

5

Edukt 3

HCID 313Hydrochloric AcidHCID 10906Tert-Butyl nitriteHCID 271299Ethyl 5-amino-1-methyl-1H-pyrazole-4-carboxylate

Produkt 1

HCID 2758821Ethyl 5-Chloro-1-methyl-1H-pyrazole-4-carboxylateAusbeute 64 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

To a mixture of t-butyl nitrite (29.5 mL, 248 mmol), cuprous chloride (17.6 g, 177.8 mmol) and anhydrous acetonitrile (490 mL) was added 5-amino-1-methyl-1H-pyrazole-4-carboxylic acid ethyl ester (25 g, 148 mmol) in portions over 30 minutes at 0° C. The reaction mixture was stirred at room temperature for 1 h, then at 65° C. for 1 h. The mixture was then poured into 6N HCl (600 mL) and extracted with dichloromethane. The aqueous phase was extracted three times with dichloromethane. The combined organic phases were concentrated in vacuo, and the crude residue was purified by flash chromatography eluting with a gradient of 0-20% ethyl acetate/hexanes, then 20% ethyl acetate/hexanes to give 5-chloro-1-methyl-1H-pyrazole-4-carboxylic acid ethyl ester (18 g, 64%).

Aufarbeitung

  1. waitat 65° C. for 1 h
  2. extractionextracted with dichloromethane
  3. extractionThe aqueous phase was extracted three times with dichloromethane
  4. concentrationThe combined organic phases were concentrated in vacuo
  5. customthe crude residue was purified by flash chromatography
  6. washeluting with a gradient of 0-20% ethyl acetate/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-0d427ae148734a7e993a433b44686154
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07728029B2

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