Thionyl Chloride → Sulcotrione

HRID 1108941Notes

Reaction equation

HRID 1108941 reaction equation
[Cl:1][C:2]1[CH:10]=[C:9]([S:11]([CH3:14])(=[O:13])=[O:12])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=O.S(Cl)(Cl)=O.[O:19]1[CH2:24][CH2:23]OCC1>CN(C)C=O>[Cl:1][C:2]1[CH:10]=[C:9]([S:11]([CH3:14])(=[O:13])=[O:12])[CH:8]=[CH:7][C:3]=1[C:4]([CH:23]1[C:24](=[O:19])[CH2:10][CH2:2][CH2:3][C:4]1=[O:6])=[O:6]

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 312751,4-DioxaneHCID 7358632-Chloro-4-(methylsulfonyl)benzoic acid

Product 1

HCID 91760Sulcotrione

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideCatalyst

Procedure

42.5 g of 2-chloro-4-methylsulfonylbenzoic acid were boiled in 160 ml of dioxane with 5 drops of dimethylformamide and 25.1 ml of thionyl chloride until the evolution of gas subsided. The solvent was stripped off with the exclusion of moisture on a rotary evaporator. To the oily residue there were added at 0° C. 19.7 g of 1,3-cyclohexanedione in 250 ml of acetonitrile, and 63.1 ml of triethylamine were then added dropwise at this temperature. Stirring was continued for 15 minutes, 15.3 ml of acetone cyanohydrin were added, and the mixture was allowed to stand overnight. The reaction mixture was concentrated under reduced pressure on a rotary evaporator, the residue was taken up in ethyl acetate/water, and the organic phase was washed with 2N hydrochloric acid. The product was extracted from the organic phase using 5% K2CO3 solution, and precipitated at a pH of 2-3 using concentrated hydrochloric acid, with cooling. After filtration with suction and drying, 48.4 g of 2-[2-chloro-4-(methylsulfonyl)benzoyl]-1,3-cyclohexanedione of melting point 141°-142° C. were obtained.

Workup

  1. customThe solvent was stripped off with the exclusion of moisture on a rotary evaporator
  2. additionTo the oily residue there were added at 0° C
  3. addition19.7 g of 1,3-cyclohexanedione in 250 ml of acetonitrile, and 63.1 ml of triethylamine were then added dropwise at this temperature
  4. addition15.3 ml of acetone cyanohydrin were added
  5. waitto stand overnight
  6. concentrationThe reaction mixture was concentrated under reduced pressure on a rotary evaporator
  7. washthe organic phase was washed with 2N hydrochloric acid
  8. extractionThe product was extracted from the organic phase
  9. customprecipitated at a pH of 2-3
  10. temperaturewith cooling
  11. filtrationAfter filtration with suction
  12. customdrying

Sources & evidence

ORD record
ord-1659c6d78f3d4e398d471c16156f8900
Source dataset
uspto-grants-1994_06
Patent number
US05318947

Reaction notes

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