Iodine → HCID 23368325, compound

HRID 1901550Notes

Reaction equation

HRID 1901550 reaction equation
[CH2:1]([O:4][C:5]1[C:9]([C:10]#[N:11])=[C:8]([S:12](C)(=O)=O)[S:7][N:6]=1)[C:2]#[CH:3].[SH-].[K+].[OH-].[K+].Cl[CH:21]([F:23])[F:22].[I:24]I.[I-].[K+]>O1CCOCC1.O.CN(C=O)C>[I:24][C:3]#[C:2][CH2:1][O:4][C:5]1[C:9]([C:10]#[N:11])=[C:8]([S:12][CH:21]([F:23])[F:22])[S:7][N:6]=1

Participants

10

Reactant 6

HCID 807IodineHCID 4875Potassium IodideHCID 6372ChlorodifluoromethaneHCID 14797Potassium Hydroxide2×HCID 102109Potassium bisulfideHCID 15278786HCID 15278786, compound

Product 1

HCID 23368325HCID 23368325, compoundYield 80%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent3×HCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent

Procedure

2.4 Grams of 3-(2-propynyloxy)-4-cyano-5-methylsulfonylisothiazole was dissolved in 50 ml of dioxane, a solution of 2 g of potassium hydrosulfide in 5 ml of water was added thereto, and then the reaction solution was stirred for 10 minutes. Thereafter, 20 g of 30% KOH was added, and chlorodifluoromethane was blown into the reaction solution for 30 minutes at room temperature with stirring. Water was added to the reaction solution, which was then extracted with ethyl acetate. The extract was washed with water, dried and concentrated under reduced pressure to obtain 2.2 g of the crude crystal of 3-(2-propynyloxy)-4-cyano-5-difluoromethylthioisothiazole. This product was dissolved in 20 ml of DMF, 4.5 g of iodine and 3.0 g of potassium iodide were added thereto with stirring, and then 7 g of 10% KOH was added dropwise with ice-cooling. After addition, the temperature of the reaction solution was returned to room temperature, and the reaction solution was stirred for 1 hour. Water was added to the reaction solution, which was then extracted with ethyl acetate. The extract was washed with water, dried and concentrated under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from ether to obtain 2.9 g of crystals having a melting point of 106° to 107° C. (yield 80%).

Workup

  1. stirringwith stirring
  2. extractionwas then extracted with ethyl acetate
  3. washThe extract was washed with water
  4. customdried
  5. concentrationconcentrated under reduced pressure
  6. customto obtain 2.2 g of the crude crystal of 3-(2-propynyloxy)-4-cyano-5-difluoromethylthioisothiazole
  7. stirringwith stirring
  8. temperaturecooling
  9. additionAfter addition
  10. customwas returned to room temperature
  11. stirringthe reaction solution was stirred for 1 hour
  12. extractionwas then extracted with ethyl acetate
  13. washThe extract was washed with water
  14. customdried
  15. concentrationconcentrated under reduced pressure
  16. customto obtain crude crystals
  17. customThe crude crystals were recrystallized from ether

Sources & evidence

ORD record
ord-665bea291c864599a16bc2b2573c687a
Source dataset
uspto-grants-1996_11
Patent number
US05578622

Reaction notes

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