Dimethyl Sulfoxide → Isopropyl (1,3-dithiolan-2-ylidene)-(4-fluorophenyl)-acetate

HRID 620067Notes

Reaction equation

HRID 620067 reaction equation
[CH3:1][S:2]([CH3:4])=O.[H-].[Na+].[F:7][C:8]1[CH:13]=[CH:12][C:11]([CH2:14][C:15]([O:17][CH:18]([CH3:20])[CH3:19])=[O:16])=[CH:10][CH:9]=1.BrCCBr.[C:25](=S)=[S:26]>O.CCOCC>[S:2]1[CH2:4][CH2:25][S:26][C:1]1=[C:14]([C:11]1[CH:10]=[CH:9][C:8]([F:7])=[CH:13][CH:12]=1)[C:15]([O:17][CH:18]([CH3:20])[CH3:19])=[O:16]

Participants

8

Reactant 5

HCID 679Dimethyl SulfoxideHCID 6348Carbon DisulfideHCID 78391,2-DibromoethaneHCID 24758Sodium hydrideHCID 23038995Isopropyl 4-fluorophenylacetate

Product 1

HCID 53915256Isopropyl (1,3-dithiolan-2-ylidene)-(4-fluorophenyl)-acetate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

Dry dimethyl sulphoxide (180 ml) is added to sodium hydride (9.0 g, 55% dispersion in mineral oil). After 30 minutes, isopropyl 4-fluorophenylacetate (17.7 g) and carbon disulphide (8.2 g) are added. The mixture is stirred for two hours at room temperature. 1,2-Dibromoethane (18.6 g) is then slowly added. The reaction is exothermic and the temperature is maintained below 30°. The mixture is stirred for one hour, and then ether (200 ml) is added. After cooling to 0° water (200 ml) is slowly added. The two phases are separated. The aqueous phase is extracted with ether (2×100 ml) and the combined organic solutions are washed with water (2×50 ml). After drying over magnesium sulphate, the solvent is evaporated in vacuo and the residue is recrystallised from hexane. The product is dried in vacuo to constant weight to yield isopropyl (1,3-dithiolan-2-ylidene)-(4-fluorophenyl)-acetate, m.p. 106°-107°.

Workup

  1. temperaturethe temperature is maintained below 30°
  2. stirringThe mixture is stirred for one hour
  3. additionis slowly added
  4. customThe two phases are separated
  5. extractionThe aqueous phase is extracted with ether (2×100 ml)
  6. washthe combined organic solutions are washed with water (2×50 ml)
  7. dry with materialAfter drying over magnesium sulphate
  8. customthe solvent is evaporated in vacuo
  9. customthe residue is recrystallised from hexane
  10. customThe product is dried in vacuo to constant weight

Sources & evidence

ORD record
ord-ca58426ca44648bcaf27ee969466d0c5
Source dataset
uspto-grants-1989_04
Patent number
US04818765

Reaction notes

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