Cesium fluoride → 4-(4,4'-Dichlorobiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,5-dione

HRID 1191570Notes

Reaction equation

HRID 1191570 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([Cl:20])=[C:6]([CH:8]2[C:13](=[O:14])[C:12]([CH3:16])([CH3:15])[O:11][C:10]([CH3:18])([CH3:17])[C:9]2=[O:19])[CH:7]=1.[Cl:21][C:22]1[CH:27]=[CH:26][C:25](B(O)O)=[CH:24][CH:23]=1.[F-].[Cs+]>COCCOC>[Cl:20][C:5]1[CH:4]=[CH:3][C:2]([C:25]2[CH:26]=[CH:27][C:22]([Cl:21])=[CH:23][CH:24]=2)=[CH:7][C:6]=1[CH:8]1[C:13](=[O:14])[C:12]([CH3:16])([CH3:15])[O:11][C:10]([CH3:18])([CH3:17])[C:9]1=[O:19]

Participants

5

Reactant 3

HCID 25953Cesium fluorideHCID 742994-Chlorophenylboronic acidHCID 684878854-(5-Bromo-2-chlorophenyl)-2,2,6,6-tetramethylpyran-3,5-dione

Product 1

HCID 684882904-(4,4'-Dichlorobiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,5-dioneYield 34.1%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-(5-bromo-2-chlorophenyl)-2,2,6,6-tetramethylpyran-3,5-dione (0.22 g, 0.6 mmol), 4-chlorophenylboronic acid (0.14 g, 0.9 mmol), and cesium fluoride (0.28 g, 1.8 mmol) are stirred together in 1,2-dimethoxyethane (2.4 ml) under an atmosphere of nitrogen at room temperature for 45 minutes. [1,1′-bis(diphenyl-phosphino)ferrocene]dichloropalladium(II) (80 mg, 0.098 mmol) is added and the reaction mixture is heated at 80° C. overnight. The reaction mixture is filtered through diatomaceous earth, washing the filter cake with dichloromethane (7 ml) and water (3 ml). The mixture is acidified to pH1 by addition of 2M aqueous hydrochloric acid, and the organic phase is separated. The aqueous phase is extracted with dichloromethane, and all organic extracts are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated. The residue is dissolved in N,N-dimethylformamide (approximately 1 ml) and purified by preparative reverse phase HPLC to give 4-(4,4′-dichlorobiphenyl-3-yl)-2,2,6,6-tetramethylpyran-3,5-dione (80 mg).

Workup

  1. filtrationThe reaction mixture is filtered through diatomaceous earth
  2. washwashing the filter cake with dichloromethane (7 ml) and water (3 ml)
  3. additionThe mixture is acidified to pH1 by addition of 2M aqueous hydrochloric acid
  4. customthe organic phase is separated
  5. extractionThe aqueous phase is extracted with dichloromethane
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customthe filtrate evaporated
  9. dissolutionThe residue is dissolved in N,N-dimethylformamide (approximately 1 ml)
  10. custompurified by preparative reverse phase HPLC

Sources & evidence

ORD record
ord-ecd711528c7f4e59b25aac796c3e8656
Source dataset
uspto-grants-2014_03
Patent number
US08680012B2

Reaction notes

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