Cesium carbonate → 3-Cyclopropylamino-5-phenyl-thiophene-2-carboxylic acid methyl ester

HRID 1015638

反応式

HRID 1015638 の反応式
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:8][C:9]=1Br)=[O:4].[CH:17]1([NH2:20])[CH2:19][CH2:18]1.C(=O)([O-])[O-].[Cs+].[Cs+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:8][C:9]=1[NH:20][CH:17]1[CH2:19][CH2:18]1)=[O:4]

参加物

6

反応物 4

HCID 10796Cesium carbonateHCID 69828CyclopropylamineHCID 634876Binap, (A+-)-HCID 20775762Methyl 3-bromo-5-phenyl-thiophene-2-carboxylate

生成物 1

HCID 207757643-Cyclopropylamino-5-phenyl-thiophene-2-carboxylic acid methyl ester収率 22%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
110 °C

実験手順

To a solution of 3-Bromo-5-phenyl-thiophene-2-carboxylic acid methyl ester (250 mg, 0.89 mmol) in toluene (25 ml) was added cyclopropylamine (57 mg, 1.0 mmol), cesium carbonate (382 mg, 1.2 mmol), BINAP (50 mg, 0.08 mmol) and tris (dibenzyli-denacetone)dipaladium (0) (38 mg, 0.04 mmol). The reaction mixture was stirred for 16 h at 110° C. in a sealed tube. The mixture was partitioned between toluene (20 mL) and water (20 mL) and the organic layer was separated. The aqueous phase was washed twice with toluene (2×10 mL) and the combined toluene layer was dried (MgSO4), concentrated and the residue was purified by preparative chromatography (10% EtOAc/Hexane) to obtain 52 mg (22%) of 3-Cyclopropylamino-5-phenyl-thiophene-2-carboxylic acid methyl ester. NMR 1H (CDCl3, 400 MHz): 7.67-7.62 ppm (m, 2H, Haro); 7.43-7.32 ppm (m, 3H, Haro); 7.16 ppm (s, 1H, Haro); 3.82 ppm (S, 3H); 2.65 ppm (m, 1H); 0.62 ppm (m, 2H); 0.35 ppm (m, 2H).

後処理

  1. customThe mixture was partitioned between toluene (20 mL) and water (20 mL)
  2. customthe organic layer was separated
  3. washThe aqueous phase was washed twice with toluene (2×10 mL)
  4. dry with materialthe combined toluene layer was dried (MgSO4)
  5. concentrationconcentrated
  6. customthe residue was purified by preparative chromatography (10% EtOAc/Hexane)

出典と根拠

ORDレコード
ord-78c2b097b9ca481783350ce25cc76f74
出典データセット
uspto-grants-2011_07
特許番号
US07985769B2

関連ノート

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