Water → HCID 12111908, compound

HRID 2121709Notes

Reaction equation

HRID 2121709 reaction equation
[C:1]([C:4]1[C:8]([CH3:9])=[C:7]([Cl:10])[S:6][C:5]=1[Cl:11])(=[O:3])[CH3:2].[N:12]1[CH:17]=[CH:16][C:15](B(O)O)=[CH:14][CH:13]=1.O.C(=O)(O)[O-].[Na+]>COCCOC.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[C:1]([C:4]1[C:8]([CH3:9])=[C:7]([Cl:10])[S:6][C:5]=1[Cl:11])(=[O:3])[CH3:2].[C:1]([C:4]1[C:8]([CH3:9])=[C:7]([C:15]2[CH:16]=[CH:17][N:12]=[CH:13][CH:14]=2)[S:6][C:5]=1[C:15]1[CH:16]=[CH:17][N:12]=[CH:13][CH:14]=1)(=[O:3])[CH3:2]

Participants

8

Reactant 4

HCID 962WaterHCID 516892Sodium Bicarbonate2×HCID 2734379(Pyridin-4-yl)boronic acid2×HCID 12112791HCID 12112791, compound

Product 2

HCID 12111908HCID 12111908, compoundHCID 12112791HCID 12112791, compound

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalyst2×HCID 80711,2-DimethoxyethaneSolvent

Procedure

3-Acetyl-2,5-dichloro-4-methylthiophene was prepared according the method of Eric C. Bigham, U.S. Pat. No. 4,110,342 (1978). To a stirred solution of 3-acetyl-2,5-dichloro-4-methylthiophene (593 mg, 2.84 mmol) in DME (15 mL) were added 4-pyridineboronic acid (0.87 g, 7.09 mmol). water (5 mL), sodium bicarbonate (1.76 g, 20.9 mmol) and bis(triphenylphosphine)-palladium(II)chloride (0.2 g, 0.28 mmol) at room temperature under nitrogen. The mixture was heated at reflux temperature for 8 hours. After cooling, 4-pyridineboronic acid (0.3 g, 2.44 mmol), sodium bicarbonate (0.6 g, 7.14 mmol) and bis(triphenylphosphine)-palladium(II)chloride (0.1 g, 0.14 mmol) were added to the reaction mixture. The mixture was heated at reflux temperature for additional 3 hours. After cooling, the reaction mixture was filtered through celite pad. The filtrate was extracted with ethyl acetate (100 mL×2), and the combined organic layers were washed with brine, dried over MgSO4, and concentrated in vacuo. The resulting residue was purified by flash chromatography eluting with hexane-ethyl acetate (1:2) to provide the title product as a solid. Recrystallized from ethyl acetate gave the title product (468 mg, 56% yield).

Workup

  1. customat room temperature
  2. temperatureThe mixture was heated
  3. temperatureat reflux temperature for 8 hours
  4. temperatureAfter cooling
  5. temperatureThe mixture was heated
  6. temperatureat reflux temperature for additional 3 hours
  7. temperatureAfter cooling
  8. filtrationthe reaction mixture was filtered through celite pad
  9. extractionThe filtrate was extracted with ethyl acetate (100 mL×2)
  10. washthe combined organic layers were washed with brine
  11. dry with materialdried over MgSO4
  12. concentrationconcentrated in vacuo
  13. customThe resulting residue was purified by flash chromatography
  14. washeluting with hexane-ethyl acetate (1:2)

Sources & evidence

ORD record
ord-5678172d006c4aeeb178a76e85078c99
Source dataset
uspto-grants-2004_02
Patent number
US06696470B2

Reaction notes

Loading…