Acetonitrile → 3-((4-Methoxybenzyl)sulfanyl)-2,5-dimethylphenyl acetate

HRID 591418Notes

Reaction equation

HRID 591418 reaction equation
[C:1]([O:4][C:5]1[CH:10]=[C:9]([CH3:11])[CH:8]=[C:7](O)[C:6]=1[CH3:13])(=[O:3])[CH3:2].[CH3:14][C:15]#N.O([S:25]([C:28](F)(F)F)(=O)=O)S(C(F)(F)F)(=O)=O>O>[C:1]([O:4][C:5]1[CH:10]=[C:9]([CH3:11])[CH:8]=[C:7]([S:25][CH2:28][C:14]2[CH:15]=[CH:10][C:5]([O:4][CH3:1])=[CH:6][CH:7]=2)[C:6]=1[CH3:13])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 6342AcetonitrileHCID 67749Trifluoromethanesulfonic anhydrideHCID 226254043-Hydroxy-2,5-dimethylphenyl acetate

Product 1

HCID 897679303-((4-Methoxybenzyl)sulfanyl)-2,5-dimethylphenyl acetate

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of 3-hydroxy-2,5-dimethylphenyl acetate (1.04 g) and CH3CN (57 mL) were added TEA (1.61 mL) and Tf2O (1.17 mL) at 0° C. The mixture was stirred at 0° C. for 30 min under nitrogen atmosphere. The mixture was diluted with water at 0° C. and then concentrated in vacuo. The residue was extracted with EtOAc. The organic layer was washed with brine, dried over MgSO4, and concentrated in vacuo. The residual crude material was dissolved in toluene (50 mL). To the solution were added DIPEA (1.79 mL), (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (0.150 g), (4-methoxyphenyl)methanethiol (0.723 mL) and tris(dibenzylideneacetone)dipalladium (0) (Pd2(dba)3, 0.238 g) at room temperature. The mixture was refluxed for 4 h. After cooling, water was added to the mixture, and the mixture was extracted with EtOAc. The organic layer was separated, washed with brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (EtOAc/hexane) to give the title compound (1.27 g).

Workup

  1. concentrationconcentrated in vacuo
  2. extractionThe residue was extracted with EtOAc
  3. washThe organic layer was washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo
  6. dissolutionThe residual crude material was dissolved in toluene (50 mL)
  7. additionTo the solution were added DIPEA (1.79 mL), (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (0.150 g), (4-methoxyphenyl)methanethiol (0.723 mL) and tris(dibenzylideneacetone)dipalladium (0) (Pd2(dba)3, 0.238 g) at room temperature
  8. temperatureThe mixture was refluxed for 4 h
  9. temperatureAfter cooling
  10. additionwater was added to the mixture
  11. extractionthe mixture was extracted with EtOAc
  12. customThe organic layer was separated
  13. washwashed with brine
  14. dry with materialdried over MgSO4
  15. concentrationconcentrated in vacuo
  16. customThe residue was purified by silica gel column chromatography (EtOAc/hexane)

Sources & evidence

ORD record
ord-153a0f7d4a9549fbaf79f76854c5e1e3
Source dataset
uspto-grants-2016_01
Patent number
US09238639B2

Reaction notes

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