Potassium Carbonate → 5-(4-Chlorophenyl)-N-(2,2-diethoxyethyl)thiophene-2-carboxamide

HRID 2384874ノート

反応式

HRID 2384874 の反応式
[CH2:1]([O:3][CH:4]([O:15][CH2:16][CH3:17])[CH2:5][NH:6][C:7]([C:9]1[S:10][C:11](Cl)=[CH:12][CH:13]=1)=[O:8])[CH3:2].[Cl:18][C:19]1[CH:24]=[CH:23][C:22](B(O)O)=[CH:21][CH:20]=1.C(=O)([O-])[O-].[K+].[K+]>[Pd](Cl)Cl.CCO>[CH2:1]([O:3][CH:4]([O:15][CH2:16][CH3:17])[CH2:5][NH:6][C:7]([C:9]1[S:10][C:11]([C:22]2[CH:23]=[CH:24][C:19]([Cl:18])=[CH:20][CH:21]=2)=[CH:12][CH:13]=1)=[O:8])[CH3:2]

参加物

6

反応物 3

HCID 11430Potassium CarbonateHCID 742994-Chlorophenylboronic acidHCID 666738855-chloro-N-(2,2-diethoxyethyl)thiophene-2-carboxamide

生成物 1

HCID 1317294095-(4-Chlorophenyl)-N-(2,2-diethoxyethyl)thiophene-2-carboxamide収率 103.6%

試薬・触媒・溶媒 2

HCID 24290Palladium Chloride触媒HCID 702Ethanol溶媒

実験手順

Add 5-chloro-thiophene-2-carboxylic acid (2,2-diethoxyethyl) amide (50.15 g, 0.18 mol), 4-chlorophenylboronic acid (29.84 g, 0.18 mol), potassium carbonate (50 g, 0.36 mol), [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)(3-chloropyridyl)] palladium (II) dichloride (4.40 g, 0.006 mol), and EtOH (1000 mL) to a 2 L three-necked round bottom flask equipped with a overhead stirrer, reflux condenser, nitrogen inlet/outlet, addition funnel, and thermocouple. Heat the resulting slurry for 35 minutes, then add activated carbon (5.8 g) and heat for an additional 0.5 h. Filter the resulting slurry through glass microfibre filter and rinse solids with EtOH (500 mL). Remove solvent from the filtrate under reduced pressure until 15-20% solvent remains. To this filtrate, add water (1300 mL) and stir the resulting slurry at room temperature for 1 h, then at 0-5° C. for 0.5 h. Filter the slurry, rinse the solids with water (1000 mL), and dry to afford 66 g of crude 5-(4-chlorophenyl)-thiophene-2-carboxylic acid (2,2-diethyoxyethyl) amide. Reflux the crude 5-(4-chlorophenyl)-thiophene-2-carboxylic acid (2,2-diethyoxyethyl) amide in heptane (1625 mL) for 1 h then filter through a glass microfibre filter. Transfer the filtrate to a round bottom flask and remove solvent until 725 mL of solvent remained. Stir the mixture under chilled conditions for 40 min. Filter the resulting slurry, rinse with heptane (100 mL), and dry to afford 41 g (64%) as a white solid. 1H NMR (500 MHz, CDCl3): δ 7.54 (d, J=9.0 Hz, 2H), 7.45 (d, J=4.5 Hz, 1H), 7.38 (d, J=9.0 Hz, 2H), 7.24 (d, J=4.5 Hz, 1H), 6.20 (bs, 1H), 4.62 (t, J=5.5 Hz, 1H), 3.73-3.79 (m, 2H), 3.57-3.62 (m, 4H), 1.25 (t, J=7.0 Hz, 6H),

後処理

  1. customequipped with a overhead stirrer
  2. temperaturereflux
  3. additioncondenser, nitrogen inlet/outlet, addition funnel
  4. temperatureHeat the resulting slurry for 35 minutes
  5. additionadd activated carbon (5.8 g)
  6. temperatureheat for an additional 0.5 h
  7. filtrationFilter the resulting slurry through glass microfibre
  8. filtrationfilter
  9. washrinse solids with EtOH (500 mL)
  10. additionTo this filtrate, add water (1300 mL)
  11. waitat 0-5° C. for 0.5 h
  12. filtrationFilter the slurry
  13. washrinse the solids with water (1000 mL)
  14. customdry

出典と根拠

ORDレコード
ord-29c2dff66229455a94743f6b2c9744f1
出典データセット
uspto-grants-2012_09
特許番号
US08263772B2

反応ノート

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