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

HRID 2168495ノート

反応式

HRID 2168495 の反応式
CS(C)=O.C(Cl)(=O)C(Cl)=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(N(CC)C(C)C)(C)C>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

6

反応物 4

HCID 679Dimethyl SulfoxideHCID 65578Oxalyl chlorideHCID 81531DiisopropylethylamineHCID 66899478methyl 1-(2-hydroxyethyl)-1H-indazole-7-carboxylate

生成物 1

HCID 86672700methyl 1-(2-oxoethyl)-1H-indazole-7-carboxylate収率 53%

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

To a stirred solution of DMSO (0.4 mL, 5.2 mmol) and methylene chloride (2 mL) at −78° C. was added oxalyl chloride (0.3 mL, 3.1 mmol) dropwise. After 20 min, a solution of methyl 1-(2-hydroxyethyl)-1H-indazole-7-carboxylate (0.6 g, 2.6 mmol) from Step D above in methylene chloride (17 mL) was added and the mixture was stirred at −78° C. for 1.5 h. After N,N-diisopropylethylamine was added, the reaction was cooled to 0° C. and quenched with saturated aqueous ammonium chloride. The aqueous layer was extracted with methylene chloride and the organic extracts were dried (Na2SO4), filtered, concentrated under reduced pressure and purified by preparatory thin layer chromatography (30% ethyl acetate in hexanes) to give methyl 1-(2-oxoethyl)-1H-indazole-7-carboxylate (0.3 g, 53%): 1H NMR (500 MHz, CDCl3) δ 9.79 (s, 1H), 8.16 (s, 1H), 8.10-8.09 (m, 1H), 7.99-7.97 (m, 1H), 7.25-7.21 (m, 1H), 5.61 (s, 2H), 3.92 (s, 3H).

後処理

  1. temperaturethe reaction was cooled to 0° C.
  2. customquenched with saturated aqueous ammonium chloride
  3. extractionThe aqueous layer was extracted with methylene chloride
  4. dry with materialthe organic extracts were dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. custompurified by preparatory thin layer chromatography (30% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-5236beb998884c6799cd03a85c41eee7
出典データセット
uspto-grants-2015_06
特許番号
US09045501B2

反応ノート

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