Dimethylformamide → ethyl 5-formyl-1H-pyrrole-2-carboxylate

HRID 1372381ノート

反応式

HRID 1372381 の反応式
CN(C)[CH:3]=[O:4].P(Cl)(Cl)(Cl)=O.[NH:11]1[CH:15]=[CH:14][CH:13]=[C:12]1[C:16]([O:18][CH2:19][CH3:20])=[O:17].[OH-].[Na+]>ClC(Cl)C>[CH2:19]([O:18][C:16]([C:12]1[NH:11][C:15]([CH:3]=[O:4])=[CH:14][CH:13]=1)=[O:17])[CH3:20].[CH2:19]([O:18][C:16]([C:12]1[NH:11][CH:15]=[C:14]([CH:3]=[O:4])[CH:13]=1)=[O:17])[CH3:20]

参加物

7

反応物 4

HCID 6228DimethylformamideHCID 14798Sodium HydroxideHCID 24813Phosphorus oxychlorideHCID 255670Ethyl 1H-pyrrole-2-carboxylate

生成物 2

HCID 321485ethyl 5-formyl-1H-pyrrole-2-carboxylate収率 50%HCID 321486Ethyl 4-formyl-1H-pyrrole-2-carboxylate収率 7%

試薬・触媒・溶媒 1

HCID 63651,1-Dichloroethane溶媒3 回

実験手順

To a solution of dimethylformamide (21 mL, 0.27 mol) in 75 mL of dichloroethane was added a solution of phosphorus oxychloride (25 mL, 0.27 mol) in 75 mL of dichloroethane at 0° C. The mixture was stirred at room temperature for 30 minutes and cooled to 0–20 C. To the mixture was added a solution of ethyl pyrrole-2-carboxylate (25 g, 0.18 mol) in 50 mL of dichloroethane dropwise. The resulting mixture was stirred at room temperature for 30 minutes and then at 40° C. for 1 hour. The mixture was poured into ice and basified to pH 11 with 5 N sodium hydroxide solution. The mixture was extracted with ethyl acetate and the extract washed with water and brine and dried over anhydrous sodium sulfate. The two products were separated by column chromatography (1:3 ethyl acetate:hexane) to give 15 g (50% yield) of 5-formyl-1H-pyrrole-2-carboxylic acid ethyl ester and 2 g (7% yield) of 4-formyl-1H-pyrrole-2-carboxylic acid ethyl ester. 1H-NMR (300 MHz, dimethylsulfoxide) δ 13.02 (br s, 1H, NH), 9.69 (s, 1H, CHO), 6.95 (d, 1H), 6.86 (d, 1H), 4.27 (q, 2H, CH3), 1.28 (t, 3H, CH3). MS m/z 167 [M+].

後処理

  1. temperaturecooled to 0–20 C
  2. stirringThe resulting mixture was stirred at room temperature for 30 minutes
  3. waitat 40° C. for 1 hour
  4. extractionThe mixture was extracted with ethyl acetate
  5. washthe extract washed with water and brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. customThe two products were separated by column chromatography (1:3 ethyl acetate:hexane)

出典と根拠

ORDレコード
ord-a624f4f9254e49509def5bd3cb869b66
出典データセット
uspto-grants-2007_01
特許番号
US07157577B2

反応ノート

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