Dimethyl Sulfoxide → methyl 1-(2-oxoethyl)-1H-indazole-7-carboxylate

HRID 2369935Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2369935
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][CH2:12][CH2:13][N:14]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][C:21]=2[C:23]([O:25][CH3:26])=[O:24])[CH:16]=[N:15]1>C(Cl)Cl>[O:11]=[CH:12][CH2:13][N:14]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][C:21]=2[C:23]([O:25][CH3:26])=[O:24])[CH:16]=[N:15]1

Komponenten

5

Edukt 3

HCID 679Dimethyl SulfoxideHCID 65578Oxalyl chlorideHCID 66899478methyl 1-(2-hydroxyethyl)-1H-indazole-7-carboxylate

Produkt 1

HCID 86672700methyl 1-(2-oxoethyl)-1H-indazole-7-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

Oxalyl chloride (1.3 mL, 15.5 mmol) was added dropwise to a mixture of dimethyl sulfoxide (1.8 mL, 25.8 mmol) and methylene chloride (4 mL) at −78° C. After addition was complete, the mixture was stirred at −78° C. for 30 min. A solution of methyl 1-(2-hydroxyethyl)-1H-indazole-7-carboxylate (2.8 g, 12.9 mmol) from Step D above in methylene chloride (40 mL) and added dropwise while maintaining the temperature at −78° C. The reaction was then stirred at −78° C. for 1-2 h. The reaction was quenched with N,N-diisopropylethylamine, cooled to 0° C., and sat. NaHCO3 was added. The aqueous phase was extracted several times with methylene chloride and the combined organic layers were dried (Na2SO4), filtered and concentrated to give methyl 1-(2-oxoethyl)-1H-indazole-7-carboxylate as a yellow oil (3.8 g, crude): 1H NMR (300 MHz, CDCl3) δ 9.79 (s, 1H), 8.16 (s, 1H), 8.14-8.08 (m, 2H), 7.98 (d, J=7.5 Hz, 1H), 5.61 (s, 2H), 3.99 (s, 3H); MS (ESI+) m/z 219 (M+H).

Aufarbeitung

  1. additionAfter addition
  2. temperaturewhile maintaining the temperature at −78° C
  3. stirringThe reaction was then stirred at −78° C. for 1-2 h
  4. customThe reaction was quenched with N,N-diisopropylethylamine
  5. temperaturecooled to 0° C.
  6. additionsat. NaHCO3 was added
  7. extractionThe aqueous phase was extracted several times with methylene chloride
  8. dry with materialthe combined organic layers were dried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-76858a79911b45cf8c06ff362ea9e0d6
Quelldatensatz
uspto-grants-2014_04
Patentnummer
US08710046B2

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