Potassium Carbonate → 5-Cyclohex-1-enyl-6-(2,2,2-trifluoroethoxy)nicotinic acid methylester

HRID 240696

反応式

HRID 240696 の反応式
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[N:7][C:8]([O:12][CH2:13][C:14]([F:17])([F:16])[F:15])=[C:9](Br)[CH:10]=1)=[O:4].C(=O)([O-])[O-].[K+].[K+].[C:24]1(B2OC(C)(C)C(C)(C)O2)[CH2:29][CH2:28][CH2:27][CH2:26][CH:25]=1>CN(C=O)C>[CH3:1][O:2][C:3]([C:5]1[CH:6]=[N:7][C:8]([O:12][CH2:13][C:14]([F:17])([F:16])[F:15])=[C:9]([C:24]2[CH2:29][CH2:28][CH2:27][CH2:26][CH:25]=2)[CH:10]=1)=[O:4]

参加物

5

反応物 3

HCID 11430Potassium CarbonateHCID 109326752-(Cyclohex-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 66686828Methyl 5-bromo-6-(2,2,2-trifluoroethoxy)nicotinate

生成物 1

HCID 712944455-Cyclohex-1-enyl-6-(2,2,2-trifluoroethoxy)nicotinic acid methylester収率 85.8%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

5-Bromo-6-(2,2,2-trifluoroethoxy)-3-pyridinecarboxylic acid methyl ester (500 mg, 1.59 mmol, CAN 1211589-51-3), potassium carbonate (660 mg, 4.78 mmol) and 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (65.0 mg, 79.6 μmol) were combined to give a light red solid. To this solid was added a solution of 2-(1-cyclohexen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (331 mg, 1.59 mmol, CAN 141091-37-4) in DMF (12.0 ml), that had been thoroughly degassed and flushed with argon. The reaction mixture was heated to 80° C. and stirred for 48 h. Subsequently the reaction mixture was cooled to ambient temperature and poured into 75 mL brine and extracted with isopropyl acetate (2×150 mL). The organic layers were washed with brine (2×50 mL), combined and dried with Na2SO4 and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, 50 g, 0% to 10%, n-heptane/isopropyl acetate) to give the title compound (0.43 g, 60%) as white solid; MS (EI) 316.3 (M+H)+.

後処理

  1. customto give a light red solid
  2. customhad been thoroughly degassed
  3. customflushed with argon
  4. temperatureSubsequently the reaction mixture was cooled to ambient temperature
  5. additionpoured into 75 mL brine
  6. extractionextracted with isopropyl acetate (2×150 mL)
  7. washThe organic layers were washed with brine (2×50 mL)
  8. dry with materialdried with Na2SO4
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by flash chromatography (silica gel, 50 g, 0% to 10%, n-heptane/isopropyl acetate)

出典と根拠

ORDレコード
ord-71407f74e6494b1bbf8e5861566140cf
出典データセット
uspto-grants-2014_02
特許番号
US08648099B2

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