Water → 1-[5-(3,4-Dimethylphenyl)-4-hydroxythiophen-3-yl]ethan-1-one

HRID 239221Notes

Reaction equation

HRID 239221 reaction equation
C(Cl)(Cl)Cl.[CH3:5][C:6]1[CH:7]=[C:8]([CH:13]2[C:17]([OH:18])=[C:16]([C:19]([CH3:21])=[O:20])[CH2:15][S:14]2)[CH:9]=[CH:10][C:11]=1[CH3:12].S(Cl)(Cl)(=O)=O.O>C(O)(C)C>[CH3:5][C:6]1[CH:7]=[C:8]([C:13]2[S:14][CH:15]=[C:16]([C:19]([CH3:21])=[O:20])[C:17]=2[OH:18])[CH:9]=[CH:10][C:11]=1[CH3:12]

Participants

6

Reactant 4

HCID 962WaterHCID 6212Chloroform2×HCID 24648Sulfuryl chlorideHCID 44207282HCID 44207282, compound

Product 1

HCID 442075201-[5-(3,4-Dimethylphenyl)-4-hydroxythiophen-3-yl]ethan-1-oneYield 20%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Conditions

Temperature
-40 °C

Procedure

A chloroform (24 mL) solution of 2-(3,4-dimethylphenyl)-3-hydroxy-4-methylcarbonyl-2,5-dihydrothiophene (2.44 g, 9.82 mmol, purity: 72%) was cooled to −40° C., and to this solution, a chloroform (37 mL) solution of sulfuryl chloride (0.79 mL, 1.0 equivalent amount) was dropwise added over a period of 55 minutes, followed by stirring at −40° C. for 60 minutes. The temperature of the solution was raised to 0° C., and water (5 mL) was dropwise added over a period of 1 minute, followed by liquid separation. The obtained chloroform solution was sequentially washed with water, a saturated salt solution, a saturated sodium hydrogencarbonate aqueous solution, a saturated sodium thiosulfate aqueous solution and a saturated salt solution, and dried over anhydrous magnesium sulfate. The drying agent was removed by filtration, and the solvent was distilled off to obtain a crude product. The obtained crude product was suspended in isopropyl alcohol (37 mL) at room temperature, followed by stirring at 0° C. for 30 minutes. The formed crystals were subjected to filtration to give the desired product (0.47 g, yield: 20%) as a yellow solid. Further, the filtrate was isolated and purified by silica gel column chromatography (eluent: hexane/ethyl acetate=3/1 (v/v)) to give the desired product (0.81 g, yield: 33%) as a yellow solid (1.28 g, yield: 53%).

Workup

  1. temperatureThe temperature of the solution was raised to 0° C.
  2. customfollowed by liquid separation
  3. washThe obtained chloroform solution was sequentially washed with water
  4. dry with materiala saturated salt solution, a saturated sodium hydrogencarbonate aqueous solution, a saturated sodium thiosulfate aqueous solution and a saturated salt solution, and dried over anhydrous magnesium sulfate
  5. customThe drying agent was removed by filtration
  6. distillationthe solvent was distilled off
  7. customto obtain a crude product
  8. customThe obtained crude product
  9. stirringby stirring at 0° C. for 30 minutes
  10. filtrationThe formed crystals were subjected to filtration

Sources & evidence

ORD record
ord-4c762e01a9b2432ca54532b467a1635a
Source dataset
uspto-grants-2014_02
Patent number
US08642786B2

Reaction notes

Loading…