Water → HCID 11128457, compound

HRID 377425Notes

Reaction equation

HRID 377425 reaction equation
S(Cl)([Cl:4])(=O)=O.[F:6][C:7]([F:17])=[CH:8][CH2:9][CH2:10][S:11][C:12]1[S:13][CH:14]=[CH:15][N:16]=1.CN(C)C=O.O>C(Cl)(Cl)Cl>[Cl:4][C:14]1[S:13][C:12]([S:11][CH2:10][CH2:9][CH:8]=[C:7]([F:6])[F:17])=[N:16][CH:15]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6228DimethylformamideHCID 24648Sulfuryl chloride4×HCID 22025956HCID 22025956, compound

Product 1

HCID 11128457HCID 11128457, compoundYield 95.9%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent4×

Conditions

Temperature
45 °C

Procedure

A solution of sulfuryl chloride (0.66 g) and chloroform (2.0 ml) was added dropwise over a period of 1.5 hour to a stirred mixture of 2-(4,4-difluorobut-3-enylthio)thiazole (1.01 g), and dimethylformamide (10 ml) maintained at 45° C. under a nitrogen atmosphere and the resultant mixture stirred for a further 2.5 hour. A further aliquot of sulfuryl chloride (0.07 g) dissolved in chloroform (1.0 ml) was then added over 15 minutes and the mixture stirred at 45° C. for 16 hours. A third portion of sulfuryl chloride (0.07 g) in chloroform (1.0 ml) was added over 30 minutes with the mixture being stirred for a further 2 hours, following which a final portion of the sulfuryl chloride (0.07 g) in chloroform (1.0 ml) was added and the mixture stirred for a final period of 30 minutes. After cooling the reaction mixture to the ambient temperature water (20 ml) was added and the mixture extracted with hexane (25 ml). The pH of the aqueous portion was adjusted to pH7 with 10% sodium hydroxide solution and extracted with hexane (25 ml). The combined hexane extracts were washed with water (2×20 ml) and then dried over anhydrous magnesium sulfate. Removal of the solvent by evaporation under reduced pressure yielded of 5-chloro-2-(4,4-difluorobut-3-enylthio)thiazole (1.13 g, 88%), identical to the product of Example 3.

Workup

  1. additionwas then added over 15 minutes
  2. stirringbeing stirred for a further 2 hours
  3. additionwas added
  4. stirringthe mixture stirred for a final period of 30 minutes
  5. additionwas added
  6. extractionthe mixture extracted with hexane (25 ml)
  7. extractionextracted with hexane (25 ml)
  8. washThe combined hexane extracts were washed with water (2×20 ml)
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customRemoval of the solvent
  11. customby evaporation under reduced pressure

Sources & evidence

ORD record
ord-3f7e2931f7704f0183527dd429095924
Source dataset
uspto-grants-2000_02
Patent number
US06025497

Reaction notes

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