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

HRID 1874973노트

반응식

HRID 1874973 반응식
[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]

참가 물질

5

반응물 2

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

생성물 1

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

시약·촉매·용매 2

HCID 74505Methyltriphenyliphosphonium bromide촉매HCID 8028Tetrahydrofuran용매2회

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-8b604672ef9749a988ca3d03898cc48b
출처 데이터셋
uspto-grants-2012_11
특허 번호
US08304419B2

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