Cesium carbonate → Methyl 4-benzyloxythieno[2,3-c]pyridine-2-carboxylate

HRID 1977419ノート

反応式

HRID 1977419 の反応式
Cl[C:2]1[C:3]([CH:16]=O)=[C:4]([O:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:5]=[N:6][CH:7]=1.[C:18]([O:22][CH3:23])(=[O:21])[CH2:19][SH:20].C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCCC1>[CH2:9]([O:8][C:4]1[CH:5]=[N:6][CH:7]=[C:2]2[S:20][C:19]([C:18]([O:22][CH3:23])=[O:21])=[CH:16][C:3]=12)[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

参加物

5

反応物 3

HCID 10796Cesium carbonateHCID 16907Methyl ThioglycolateHCID 185162345-Chloro 3-benzyloxy pyridine-4-carboxaldehyde

生成物 1

HCID 18516285Methyl 4-benzyloxythieno[2,3-c]pyridine-2-carboxylate収率 55%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To an ice cold solution of Example 236B (4.2 g, 17 mmol) in anhydrous tetrahydrofuran (42 mL) under nitrogen atmosphere was added methyl thioglycolate (1.83 mL, 20.4 mmol) followed by powdered cesium carbonate (6.65 g, 20.4 mmol). Then the reaction mixture was allowed to warm to room temperature with stirring under nitrogen. After 30 minutes the reaction was refluxed for 15 minutes and cooled to room temperature. The reaction mixture was quenched with ice (50 mL) and partitioned with ethyl acetate (250 mL). The organic layer separated was washed with an ice cold solution of saturated NaCl (3×60 mL), dried (Na2SO4), and concentrated under reduced pressure to obtain the crude product which was recrystallized from methanol. The mother liquor was purified by flash chromatography on silica gel eluting with 7% acetone-hexane. The combined fractions gave the title compound in 55% yield (3.07 g). MS (APCI) m/e: 300 (M+H)+; 1H NMR (300 MHz, DMSO-d6) d: 3.92 (s, 3H), 5.42 (s, 2H), 7.35-7.47 (m, 3H), 7.52-7.57 (m, 2H, Ar—CH), 8.12 (s, 1H,), 8.36 (s, 1H), 8.98 (s, 1H).

後処理

  1. temperatureAfter 30 minutes the reaction was refluxed for 15 minutes
  2. temperaturecooled to room temperature
  3. customThe reaction mixture was quenched with ice (50 mL)
  4. custompartitioned with ethyl acetate (250 mL)
  5. customThe organic layer separated
  6. washwas washed with an ice cold solution of saturated NaCl (3×60 mL)
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated under reduced pressure
  9. customto obtain the crude product which
  10. customwas recrystallized from methanol
  11. customThe mother liquor was purified by flash chromatography on silica gel eluting with 7% acetone-hexane

出典と根拠

ORDレコード
ord-8ff2336b1bef428e9dfbb2959aac1ae6
出典データセット
uspto-grants-2001_05
特許番号
US06232320B1

反応ノート

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