methyl 3-chloro-5-formyl-1H-pyrrole-2-carboxylate → methyl 3-chloro-5-ethenyl-1H-pyrrole-2-carboxylate

HRID 1874973ノート

反応式

HRID 1874973 の反応式
[CH2:1]([Li])CCC.[Cl:6][C:7]1[CH:11]=[C:10]([CH:12]=O)[NH:9][C:8]=1[C:14]([O:16][CH3:17])=[O:15]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[Cl:6][C:7]1[CH:11]=[C:10]([CH:12]=[CH2:1])[NH:9][C:8]=1[C:14]([O:16][CH3:17])=[O:15]

参加物

5

反応物 2

HCID 86644900methyl 3-chloro-5-formyl-1H-pyrrole-2-carboxylateHCID 178418339Butyllithium

生成物 1

HCID 68485391methyl 3-chloro-5-ethenyl-1H-pyrrole-2-carboxylate収率 40.7%

試薬・触媒・溶媒 2

HCID 74505Methyltriphenyliphosphonium bromide触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

A suspension of methyl(triphenyl)phosphonium bromide (3.97 g, 11.1 mmol) in 20 mL of THF was cooled to −78° C. n-Butyllithium (1.6 M in Hexanes, 6.93 mL, 11.1 mmol) was added and the resulting yellow solution stirred for 20 minutes. A THF solution of methyl 3-chloro-5-formyl-1H-pyrrole-2-carboxylate (0.522 g, 2.78 mmol) was added and the reaction was warmed to RT. The reaction mixture was partitioned between EtOAc and water and the layers were separated. The organic layer was dried over MgSO4, filtered and the solvent evaporated. Purification was accomplished by silica gel column chromatography (EtOAc/hexanes) to afford the title compound (0.210 g, 40%) as a white solid. 1H NMR (400 MHz, Acetone-d6) δ ppm 11.05 (br. s., 1H), 6.62 (dd, 1H), 6.42 (d, 1H), 5.83 (d, 1H), 5.25 (d, 1H), 3.79 (s, 3H). LCMS: m/z=184.6 (M−1).

後処理

  1. additionwas added
  2. customThe reaction mixture was partitioned between EtOAc and water
  3. customthe layers were separated
  4. dry with materialThe organic layer was dried over MgSO4
  5. filtrationfiltered
  6. customthe solvent evaporated
  7. customPurification

出典と根拠

ORDレコード
ord-8b604672ef9749a988ca3d03898cc48b
出典データセット
uspto-grants-2012_11
特許番号
US08304419B2

反応ノート

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