Chloroform → 2-(4-t-Butylphenyl)-3-hydroxy-4-methylcarbonylthiophene

HRID 239216Notes

Reaction equation

HRID 239216 reaction equation
C(Cl)(Cl)Cl.[C:5]([C:9]1[CH:14]=[CH:13][C:12]([CH:15]2[C:19]([OH:20])=[C:18]([C:21]([CH3:23])=[O:22])[CH2:17][S:16]2)=[CH:11][CH:10]=1)([CH3:8])([CH3:7])[CH3:6].S(Cl)(Cl)(=O)=O>O>[C:5]([C:9]1[CH:10]=[CH:11][C:12]([C:15]2[S:16][CH:17]=[C:18]([C:21]([CH3:23])=[O:22])[C:19]=2[OH:20])=[CH:13][CH:14]=1)([CH3:8])([CH3:6])[CH3:7]

Participants

5

Reactant 3

HCID 6212Chloroform2×HCID 24648Sulfuryl chlorideHCID 44207041HCID 44207041, compound

Product 1

HCID 442072892-(4-t-Butylphenyl)-3-hydroxy-4-methylcarbonylthiopheneYield 87.4%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
-23 °C

Procedure

A chloroform (250 mL) solution of 2-(4-t-butylphenyl)-3-hydroxy-4-methylcarbonyl-2,5-dihydrothiophene (24.94 g, 64.6 mmol, purity: 78%) was cooled to −23° C., and to this solution, a chloroform (50 mL) solution of sulfuryl chloride (5.45 mL, 1.05 equivalent amounts) was dropwise added over a period of 27 minutes, followed by stirring at from −22 to −24° C. for 33 minutes. The temperature of the solution was raised to −3° C., and water (50 mL) was dropwise added over a period of 2.5 minutes, followed by liquid separation. The obtained chloroform solution was sequentially washed with water, a saturated salt solution, a sodium hydroxide 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 distilled in chloroform (80 mL) at 45° C., the solution was cooled to 0° C., and isopropanol (375 mL) was dropwise added, followed by stirring at 0° C. for 40 minutes. The formed crystals were subjected to filtration to give the desired product as a yellow solid (15.5 g, yield: 63%).

Workup

  1. temperatureThe temperature of the solution was raised to −3° C.
  2. customfollowed by liquid separation
  3. washThe obtained chloroform solution was sequentially washed with water
  4. dry with materiala saturated salt solution, a sodium hydroxide 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. distillationwas distilled in chloroform (80 mL) at 45° C.
  10. temperaturethe solution was cooled to 0° C.
  11. additionisopropanol (375 mL) was dropwise added
  12. stirringby stirring at 0° C. for 40 minutes
  13. filtrationThe formed crystals were subjected to filtration

Sources & evidence

ORD record
ord-8cbe0f164ead4b3fa57e1e1f2ad28b2a
Source dataset
uspto-grants-2014_02
Patent number
US08642786B2

Reaction notes

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