Acetic Anhydride → Ethyl 1H-indazole-5-carboxylate

HRID 1498898Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1498898
[NH2:1][C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][C:3]=1[CH3:13].C([O-])(=O)C.[K+].C(OC(=O)C)(=O)C.C1OCCOCCOCCOCCOCCOC1.[N:44](OCCC(C)C)=O.C(=O)(O)[O-].[Na+].O.N>C(Cl)(Cl)Cl>[NH:1]1[C:2]2[C:3](=[CH:4][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:11][CH:12]=2)[CH:13]=[N:44]1

Komponenten

9

Edukt 7

HCID 7918Acetic AnhydrideHCID 8053Isoamyl NitriteHCID 2855718-Crown-6HCID 282796Ethyl 4-amino-3-methylbenzoateHCID 516892Sodium BicarbonateHCID 517044Potassium AcetateHCID 12896473Azane;hydrate

Produkt 1

HCID 1501980Ethyl 1H-indazole-5-carboxylateAusbeute 31 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6212ChloroformLösungsmittel

Versuchsvorschrift

Ethyl 4-amino-3-methylbenzoate (12.6 g, 70.0 mmol) prepared in the Step 4-1-1 and potassium acetate (7.20 g, 73.5 mmol) were suspended in chloroform (70 ml). Acetic anhydride (14.3 g, 140 mmol) was added to the suspension, and the mixture was stirred for one hour. To the mixture, 18-crown-6 (3.70 g, 14.0 mmol) and isoamyl nitrite (18.9 g, 161 mmol) were added, and the resulting mixture was heated under reflux for 21 hours. After being allowed to cool, under an ice cooling the mixture was rendered faintly alkaline with a saturated sodium bicarbonate solution and a 25% ammonia water. The faintly alkalified mixture was subjected to extraction with chloroform, and the extract was dried over anhydrous magnesium sulfate and then concentrated. The concentrate was purified by silica gel column chromatography (n-hexane:ethyl acetate=1:1) to give the title compound (4.06 g, 31%) as a light-brown powder and ethyl 1-acetyl-1H-indazole-5-carboxylate.

Aufarbeitung

  1. temperaturethe resulting mixture was heated
  2. temperatureunder reflux for 21 hours
  3. temperatureto cool, under an ice cooling the mixture
  4. extractionThe faintly alkalified mixture was subjected to extraction with chloroform
  5. dry with materialthe extract was dried over anhydrous magnesium sulfate
  6. concentrationconcentrated
  7. customThe concentrate was purified by silica gel column chromatography (n-hexane:ethyl acetate=1:1)

Quellen und Nachweise

ORD-Eintrag
ord-e10a7e810c274fd18ab6383365f8fbb2
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09200008B2

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