Water → 3-Acetyl-2-chloropyridine

HRID 2294131Notes

Reaction equation

HRID 2294131 reaction equation
[Cl:1][C:2]1[N:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4](Cl)=[O:5].[CH3:11][Sn](C)(C)C.[F-].[K+].O>CN(C)P(N(C)C)(N(C)C)=O.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl>[C:4]([C:3]1[C:2]([Cl:1])=[N:10][CH:9]=[CH:8][CH:7]=1)(=[O:5])[CH3:11]

Participants

7

Reactant 4

HCID 962WaterHCID 11661TetramethyltinHCID 522689Potassium FluorideHCID 27745412-Chloronicotinoyl chloride

Product 1

HCID 109426973-Acetyl-2-chloropyridineYield 67.5%

Reagents, catalysts & solvents 2

HCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 12679HexamethylphosphoramideSolvent

Procedure

A mixture of 2-chloronicotinic acid chloride (8.8 g, 49.5 mmol), tetramethyltin (5.5 mL, 40 mmol) and bis(benzonitrile)palladium(II) chloride (0.385 g) in 20 mL of hexamethylphosphoramide was stirred at room temperature for 20 hours. The mixture was stirred with 50 mL of 10% potassium fluoride and then poured into 50 mL of water. The mixture was extracted with diethyl ether (4×50 mL) and the combined extracts were washed with water, saturated sodium bicarbonate and sodium chloride, dried (Na2SO4) and concentrated. The residue was purified on silica gel by column chromatography eluting with hexanes/ethyl acetate (3:1) to give 3-acetyl-2-chloropyridine (4.2 g, 27 mmol).

Workup

  1. extractionThe mixture was extracted with diethyl ether (4×50 mL)
  2. washthe combined extracts were washed with water, saturated sodium bicarbonate and sodium chloride
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customThe residue was purified on silica gel by column chromatography
  6. washeluting with hexanes/ethyl acetate (3:1)

Sources & evidence

ORD record
ord-0bd36b0ccfa347068bb8384dec0eed5e
Source dataset
uspto-grants-1997_11
Patent number
US05688795

Reaction notes

Loading…