Thiophenol → HCID 15153910, compound

HRID 2212071Notes

Reaction equation

HRID 2212071 reaction equation
C1(S)C=CC=CC=1.Cl[CH2:9][CH2:10][CH2:11][CH2:12][OH:13].C(=O)([O-])[O-].[K+].[K+].[C:20]1(C)[CH:25]=[CH:24][C:23]([S:26]([O-:29])(=[O:28])=O)=[CH:22][CH:21]=1.[NH+]1C=CC=CC=1.[O:37]1[CH:42]=[CH:41][CH2:40][CH2:39][CH2:38]1>C(#N)C.O.ClCCl>[C:23]1([S:26]([CH2:9][CH2:10][CH2:11][CH2:12][O:13][CH:38]2[CH2:39][CH2:40][CH2:41][CH2:42][O:37]2)(=[O:28])=[O:29])[CH:22]=[CH:21][CH:20]=[CH:25][CH:24]=1

Participants

9

Reactant 5

HCID 7969ThiophenolHCID 80803,4-dihydro-2H-pyranHCID 11430Potassium CarbonateHCID 135694-Chloro-1-butanolHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)

Product 1

HCID 15153910HCID 15153910, compoundYield 79.8%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of thiophenol (5.02 ml, 49 mmol), 4-chloro-1-butanol (7.33 ml, 73.5 mmol) and potassium carbonate (20.32 g, 147 mmol) in acetonitrile (5 ml) was stirred at 60° C. for 18 hours. The cooled mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were concentrated in vacuo. The residue was dissolved in methanol (10 ml) and water (2 ml) and treated with Oxone™ (45.2 g, 73.5 mmol). The reaction was stirred at room temperature for 24 hours, then filtered and concentrated in vacuo. The residue was partitioned between ethyl acetate and water. The organic layer was concentrated to give an oil which was dissolved in dichloromethane (10 ml), treated with pyridinium p-toluenesulfonate (3.69 g, 14.7 mmol) and 3,4-dihydro-2H-pyran (13.35 ml, 147 mmol) and stirred at room temperature for 18 hours. The mixture was diluted with water and the layers separated. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with 25% ethyl acetate/i-hexane, to yield the title compound as a clear oil (3.5 g, 24%).

Workup

  1. extractionextracted with ethyl acetate
  2. concentrationThe combined organic layers were concentrated in vacuo
  3. dissolutionThe residue was dissolved in methanol (10 ml)
  4. additionwater (2 ml) and treated with Oxone™ (45.2 g, 73.5 mmol)
  5. stirringThe reaction was stirred at room temperature for 24 hours
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was partitioned between ethyl acetate and water
  9. concentrationThe organic layer was concentrated
  10. customto give an oil which
  11. stirringstirred at room temperature for 18 hours
  12. customthe layers separated
  13. washThe organic layer was washed with saturated aqueous sodium hydrogen carbonate solution
  14. concentrationconcentrated in vacuo
  15. customThe residue was purified by flash column chromatography on silica gel
  16. washeluting with 25% ethyl acetate/i-hexane

Sources & evidence

ORD record
ord-a77272f0eaa349b19c2484c104b97f5f
Source dataset
uspto-grants-2006_09
Patent number
US07101892B2

Reaction notes

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