Oxalyl chloride → HCID 22632919, compound

HRID 2270218Notes

Reaction equation

HRID 2270218 reaction equation
[Cl:1][C:2]1[C:7]([C:8]([OH:10])=O)=[CH:6][C:5]([F:11])=[C:4]([Cl:12])[N:3]=1.C(Cl)(=O)C(Cl)=O.Cl.[CH2:20]([O:27][NH2:28])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>CN(C=O)C.ClCCl.C(OCC)(=O)C.C(N(CC)CC)C>[CH2:20]([O:27][NH:28][C:8]([C:7]1[C:2]([Cl:1])=[N:3][C:4]([Cl:12])=[C:5]([F:11])[CH:6]=1)=[O:10])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

8

Reactant 3

HCID 65578Oxalyl chlorideHCID 102312Benzyloxyamine hydrochlorideHCID 27336592,6-Dichloro-5-fluoronicotinic acid

Product 1

HCID 22632919HCID 22632919, compoundYield 49.6%

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 8471TriethylamineCatalystHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of 2,6-dichloro-5-fluoro-3-pyridinecarboxylic acid (20.00 g, 95.2 mmol) and a few drops of DMF in dichloromethane (200 mL) was added oxalyl chloride (24.6 mL, 0.282 mol) dropwise. The mixture was stirred at room temperature until evolution of gas ceased, and the reaction mixture was evaporated under reduced pressure to remove excess of the reagent. The residue was dissolved in dichloromethane (200 mL) and O-benzylhydroxylamine hydrochloride (16.71 g, 0.105 mol) in dichloromethane (200 mL) and triethylamine (15.90 mL, 0.114 mmol) were added dropwise at 0° C. The mixture was stirred at room temperature for 3 hours, diluted with ethyl acetate (100 mL), washed with saturated aqueous sodium hydrogen carbonate, water, and dried on sodium sulfate. The solid residue was recrystallized from chloroform to give 14.87 g of the title compound as solid, mp 176-177° C.

Workup

  1. customthe reaction mixture was evaporated under reduced pressure
  2. customto remove excess of the reagent
  3. dissolutionThe residue was dissolved in dichloromethane (200 mL)
  4. stirringThe mixture was stirred at room temperature for 3 hours
  5. washwashed with saturated aqueous sodium hydrogen carbonate, water
  6. customdried on sodium sulfate
  7. customThe solid residue was recrystallized from chloroform

Sources & evidence

ORD record
ord-55e9e991411241e69c9d369c7f50eb12
Source dataset
uspto-grants-2001_12
Patent number
US06331538B1

Reaction notes

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