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

HRID 2369935ノート

反応式

HRID 2369935 の反応式
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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-78 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-76858a79911b45cf8c06ff362ea9e0d6
出典データセット
uspto-grants-2014_04
特許番号
US08710046B2

反応ノート

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