Cerium(III) chloride → 5-Bromo-2-chlorophenyl 6-ethyl-3-pyridyl ketone

HRID 1625899Notes

Reaction equation

HRID 1625899 reaction equation
Br[C:2]1[N:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[C:14]([Br:16])[CH:13]=[CH:12][C:11]=2[Cl:17])=[O:9])=[CH:4][CH:3]=1.[CH2:18]([Al](CC)CC)[CH3:19].[Cl-].[Ce+3].[Cl-].[Cl-].C(=O)([O-])O.[Na+]>O1CCCC1.CO.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>[CH2:18]([C:2]1[N:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[C:14]([Br:16])[CH:13]=[CH:12][C:11]=2[Cl:17])=[O:9])=[CH:4][CH:3]=1)[CH3:19]

Participants

8

Reactant 4

HCID 24636Cerium(III) chlorideHCID 516892Sodium BicarbonateHCID 16682930TriethylaluminumHCID 469303355-Bromo-2-chlorophenyl 6-bromo-3-pyridyl ketone

Product 1

HCID 469305245-Bromo-2-chlorophenyl 6-ethyl-3-pyridyl ketone

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
30 °C

Procedure

5-Bromo-2-chlorophenyl 6-bromo-3-pyridyl ketone (3.2 g) from Reference Example 135-(2) was dissolved in tetrahydrofuran (80 ml), and added thereto were triethylaluminium (1.0 M hexane solution, 9.9 ml), tetrakis(triphenylphosphine)palladium(0) (570 mg) and cerium(III) chloride (7.3 g), and the mixture was stirred at 30° C. for 1.5 hours. The reaction mixture was diluted with methanol, and the reaction solution was basified with a saturated aqueous sodium hydrogen carbonate solution. The insoluble materials were filtered off and, the filtrate was extracted with ethyl acetate and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate=99:1-85:15) to give 5-bromo-2-chlorophenyl 6-ethyl-3-pyridyl ketone (1.98 g) as a colorless solid. APCI-Mass m/Z 324/326 (M+H).

Workup

  1. additionadded
  2. filtrationThe insoluble materials were filtered off
  3. extractionthe filtrate was extracted with ethyl acetate
  4. dry with materialdried over magnesium sulfate
  5. customThe solvent was evaporated under reduced pressure
  6. customthe residue was purified by silica gel column chromatography (hexane:ethyl acetate=99:1-85:15)

Sources & evidence

ORD record
ord-c2a76b2f07c14be89bdb805626d87be4
Source dataset
uspto-grants-2014_07
Patent number
US08785403B2

Reaction notes

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