Methyl 4-bromobenzoate → Methyl 4-pyridin-3-ylbenzoate

HRID 352721ノート

反応式

HRID 352721 の反応式
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.C(B(CC)[C:15]1[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=1)C.[OH-].[K+].[Cl-].[NH4+]>O1CCCC1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(OCC)(=O)C.O>[N:17]1[CH:18]=[CH:19][CH:20]=[C:15]([C:2]2[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=2)[CH:16]=1

参加物

10

反応物 4

HCID 12081Methyl 4-bromobenzoateHCID 14797Potassium HydroxideHCID 25517Ammonium ChlorideHCID 6428513-(Diethylboryl)pyridine

生成物 1

HCID 4133187Methyl 4-pyridin-3-ylbenzoate収率 52.8%

試薬・触媒・溶媒 5

HCID 74236Tetrabutylammonium Bromide触媒HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

In tetrahydrofuran (100 ml), methyl 4-bromobenzoate (5.04 g) and diethyl-3-pyridylborane (Chem. Pharm. Bull., 33, 4755, 1985) (2.30 g) were dissolved, followed by the addition of tetrabutylammonium bromide (2.51 g), potassium hydroxide (2.63 g), tetrakis(triphenylphosphine)palladium (O) (1.8 g) and water (1 ml) under an argon atmosphere. The resulting mixture was heated under reflux for 2 hours. After ice cooling, an aqueous ammonium chloride solution and ethyl acetate were added to the reaction mixture. The organic layer so separated was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by chromatography on a silica gel column (hexane: ethyl acetate=1:1). The solvent was then distilled off. To the residue, methanol and IN aqueous hydrochloric acid in ethanol were added. The solvent was distilled off again. Tetrahydrofuran was added to the residue and the solid so precipitated was collected by filtration. After drying, the title compound (1.76 g, 45%) was obtained as a colorless solid.

後処理

  1. temperatureThe resulting mixture was heated
  2. temperatureunder reflux for 2 hours
  3. customThe organic layer so separated
  4. dry with materialwas dried over anhydrous magnesium sulfate
  5. customThe residue obtained
  6. distillationby distilling off the solvent
  7. customwas purified by chromatography on a silica gel column (hexane: ethyl acetate=1:1)
  8. distillationThe solvent was then distilled off
  9. additionTo the residue, methanol and IN aqueous hydrochloric acid in ethanol were added
  10. distillationThe solvent was distilled off again
  11. additionTetrahydrofuran was added to the residue
  12. customthe solid so precipitated
  13. filtrationwas collected by filtration
  14. customAfter drying

出典と根拠

ORDレコード
ord-25f2dd75016941328bf92f8e2b8329ca
出典データセット
uspto-grants-2004_06
特許番号
US06747023B1

反応ノート

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