Water → Flupyradifurone

HRID 1952248Notes

Reaction equation

HRID 1952248 reaction equation
O.[Cl:2][C:3]1[N:8]=[CH:7][C:6]([CH2:9][NH:10][CH2:11][CH:12]([F:14])[F:13])=[CH:5][CH:4]=1.[CH2:15]1[C:20](=[O:21])[O:19][CH2:18][C:16]1=O>C1(C)C=CC=CC=1.C1(C)C=CC(S(O)(=O)=O)=CC=1>[Cl:2][C:3]1[N:8]=[CH:7][C:6]([CH2:9][N:10]([CH2:11][CH:12]([F:14])[F:13])[C:16]2[CH2:18][O:19][C:20](=[O:21])[CH:15]=2)=[CH:5][CH:4]=1

Participants

6

Reactant 3

HCID 962WaterHCID 521261Tetronic acidHCID 44604123N-[(6-chloropyridin-3-yl)methyl]-2,2-difluoroethanamine

Product 1

HCID 16752772FlupyradifuroneYield 52%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 1140TolueneSolvent

Procedure

On a water separator, 21.90 g (106.0 mmol) of N-[(6-chloropyridin-3-yl)methyl]-2,2-difluoroethane-1-amine (III-1), 14.85 g (148.4 mmol) of tetronic acid and 183 mg (1.1 mmol) of 4-toluenesulphonic acid in 250 ml of toluene are heated under reflux for 2 hours. The reaction mixture is concentrated under reduced pressure, the residue is then taken up in ethyl acetate and the mixture is washed successively twice with 1 N aqueous hydrochloric acid, twice with 1 N aqueous sodium hydroxide solution and once with saturated sodium chloride solution. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. Purification of the residue by column chromatography on silica gel (silica gel 60—Merck, particle size: 0.04 to 0.063 mm) using the mobile phase ethyl acetate gives 15.9 g (52% of theory) of 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one.

Workup

  1. temperatureunder reflux for 2 hours
  2. concentrationThe reaction mixture is concentrated under reduced pressure
  3. washthe mixture is washed successively twice with 1 N aqueous hydrochloric acid, twice with 1 N aqueous sodium hydroxide solution and once with saturated sodium chloride solution
  4. dry with materialThe organic phase is dried over sodium sulphate
  5. concentrationconcentrated under reduced pressure
  6. customPurification of the residue by column chromatography on silica gel (silica gel 60—Merck, particle size: 0.04 to 0.063 mm)

Sources & evidence

ORD record
ord-5f8549eb27da4c79960216b445de1873
Source dataset
uspto-grants-2013_03
Patent number
US08404855B2

Reaction notes

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