Sodium Carbonate → HCID 66743830、化合物

HRID 2364042ノート

反応式

HRID 2364042 の反応式
Br[C:2]1[S:6][C:5]([C:7]([NH2:9])=[O:8])=[C:4]([NH:10][CH2:11][CH3:12])[CH:3]=1.[F:13][C:14]([F:20])([F:19])[CH2:15][C:16](=O)[CH3:17].CC1(C)C2(CS(O)(=O)=O)C(CC1CC2)=O.[O-]S([O-])(=O)=O.[Mg+2].C([O-])(O)=O.[Na+].[CH3:47][C:48]1[C:52](B2OC(C)(C)C(C)(C)O2)=[CH:51][N:50](C(OC(C)(C)C)=O)[N:49]=1.C(=O)([O-])[O-].[Na+].[Na+]>O.COCCOC.CC(N(C)C)=O>[CH2:11]([N:10]1[C:4]2[CH:3]=[C:2]([C:52]3[CH:51]=[N:50][NH:49][C:48]=3[CH3:47])[S:6][C:5]=2[C:7](=[O:8])[NH:9][C:16]1([CH3:17])[CH2:15][C:14]([F:20])([F:19])[F:13])[CH3:12]

参加物

11

反応物 7

HCID 10340Sodium CarbonateHCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 24083Sulfuric acid magnesium salt (1:1)HCID 516892Sodium BicarbonateHCID 5390014,4,4-Trifluorobutan-2-oneHCID 53216815Tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-YL)-1H-pyrazole-1-carboxylateHCID 66743701HCID 66743701、化合物

生成物 1

HCID 66743830HCID 66743830、化合物収率 10%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 80711,2-Dimethoxyethane溶媒HCID 31374Dimethylacetamide溶媒

反応条件

温度
100 °C

実験手順

A mixture of 5-bromo-3-(ethylamino)thiophene-2-carboxamide (250 mg, 1.0 mmol), 4,4,4-trifluorobutan-2-one (1.0 mL), CSA (23 mg, 0.10 mmol), MgSO4 (192 mg, 2.0 mmol) and DMA (0.5 mL) was microwave-irradiated at 150° C. for 1 h. The mixture was poured into saturated aqueous NaHCO3. The organic materials were extracted with EtOAc. The combined extracts were washed with water and brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 90:10 hexane/EtOAc to 50:50 hexane/EtOAc) to give a brown crystalline solid. A flask was charged with this solid, 1,2-dimethoxyethane (3 mL), tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate (555 mg, 1.8 mmol), sodium carbonate (180 mg, 3.0 mmol) and water (1.5 mL). The flask was purged with argon. Then, 1,1′-bis(diphenylphosphino)ferrocenepalladium (II) dichloride dichloromethane adduct (49 mg, 0.060 mmol) was added to the mixture. The flask was purged with argon again. After stirring at 100° C. for 6 h, organic materials were extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 50:50 hexane/EtOAc to EtOAc), then crystallized from MeOH/EtOAc/heptane) to give the title compound (37 mg, 10%) as a pale brown solid:

後処理

  1. customwas microwave-irradiated at 150° C. for 1 h
  2. extractionThe organic materials were extracted with EtOAc
  3. washThe combined extracts were washed with water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customAfter removal of the solvent at reduced pressure
  7. customthe residue was purified by column chromatography (Purif, silica gel, 90:10 hexane/EtOAc to 50:50 hexane/EtOAc)
  8. customto give a brown crystalline solid
  9. customThe flask was purged with argon
  10. customThe flask was purged with argon again
  11. extractionorganic materials were extracted with EtOAc
  12. washThe combined extracts were washed with brine
  13. dry with materialdried over Na2SO4
  14. filtrationfiltered
  15. customAfter removal of the solvent at reduced pressure
  16. customthe residue was purified by column chromatography (Purif, silica gel, 50:50 hexane/EtOAc to EtOAc)
  17. customcrystallized from MeOH/EtOAc/heptane)

出典と根拠

ORDレコード
ord-e4328937ae2b44d2b0dcc9bd1b74da08
出典データセット
uspto-grants-2014_04
特許番号
US08691828B2

反応ノート

読み込み中…