Tetrafluoroboric acid → 4-Chloro-5-(4-cyano-6-trifluoromethyl-pyridin-3-yl)-2-methoxy-benzoic acid

HRID 1486003ノート

反応式

HRID 1486003 の反応式
[C:1]([C:4]1[C:5]([O:14][CH3:15])=[CH:6][C:7]([Cl:13])=[C:8](B(O)O)[CH:9]=1)([OH:3])=[O:2].Br[C:17]1[C:22]([C:23]#[N:24])=[CH:21][C:20]([C:25]([F:28])([F:27])[F:26])=[N:19][CH:18]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[H+].[B-](F)(F)(F)F>C(OCC)(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Cl:13][C:7]1[C:8]([C:17]2[CH:18]=[N:19][C:20]([C:25]([F:27])([F:28])[F:26])=[CH:21][C:22]=2[C:23]#[N:24])=[CH:9][C:4]([C:1]([OH:3])=[O:2])=[C:5]([O:14][CH3:15])[CH:6]=1

参加物

8

反応物 5

HCID 28118Tetrafluoroboric acidHCID 62657Potassium Phosphate, TribasicHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 441195965-Borono-4-chloro-2-methoxybenzoic acidHCID 569733155-Bromo-2-(trifluoromethyl)isonicotinonitrile

生成物 1

HCID 686021944-Chloro-5-(4-cyano-6-trifluoromethyl-pyridin-3-yl)-2-methoxy-benzoic acid収率 44.4%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8857Ethyl Acetate溶媒

実験手順

N2 was bubbled through a solution of THF (8 mL) and water (2 mL) containing 5-carboxy-2-chloro-4-methoxy-phenylboronic acid (460.8 mg, 2.0 mmol) and 5-bromo-2-trifluoromethyl-isonicotinonitrile 1-1 (478 mg, 1.9 mmol) for 10 minutes. K3PO4 (1.2 g, 5.7 mmol), t-Bu3P.HBF4 (82.7 mg, 0.28 mmol), and Pd2dba3 (91.0 mg, 0.1 mmol) were added under N2 atmosphere. The mixture was sealed, stirred at rt for 3 hrs, and diluted with ethyl acetate. The organic layer was separated, washed with brine, dried over MgSO4, filtered and concentrated. The residue was purified via silica gel flash column chromatography eluting with 10% MeOH in dichloromethane to give 4-chloro-5-(4-cyano-6-trifluoromethyl-pyridin-3-yl)-2-methoxy-benzoic acid (301 mg).

後処理

  1. customN2 was bubbled through a solution of THF (8 mL) and water (2 mL)
  2. customThe mixture was sealed
  3. customThe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified via silica gel flash column chromatography
  9. washeluting with 10% MeOH in dichloromethane

出典と根拠

ORDレコード
ord-d1182e132d2d4442861ece9bfea22995
出典データセット
uspto-grants-2016_08
特許番号
US09422310B2

反応ノート

読み込み中…