Ethyl Acetate → S-[2-[4-[(Methylsulfonyl)oxy]phenyl]ethyl] ethanethioate

HRID 709442Notes

Reaction equation

HRID 709442 reaction equation
[C:1]([OH:4])(=[S:3])[CH3:2].C([O-])([O-])=O.[Cs+].[Cs+].CS(O[CH2:16][CH2:17][C:18]1[CH:23]=[CH:22][C:21]([O:24][S:25]([CH3:28])(=[O:27])=[O:26])=[CH:20][CH:19]=1)(=O)=O.CCOC(C)=O>CO.CN(C=O)C.[Cl-].[Na+].O>[CH3:28][S:25]([O:24][C:21]1[CH:22]=[CH:23][C:18]([CH2:17][CH2:16][S:3][C:1](=[O:4])[CH3:2])=[CH:19][CH:20]=1)(=[O:27])=[O:26]

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 112201221-(Methylsulfonyloxy)-2-[4-(methylsulfonyloxy)phenyl]ethaneHCID 178418634HCID 178418634, compound2×

Product 1

HCID 86650296S-[2-[4-[(Methylsulfonyl)oxy]phenyl]ethyl] ethanethioate

Reagents, catalysts & solvents 3

HCID 887MethanolSolvent2×HCID 6228DimethylformamideSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

Thioacetic acid (0.28 g, 3.73 mmol) was dissolved in anhydrous MeOH (3 mL) and Cs2CO3 (1.10 g, 3.39 mmol) was added. After 15 min. stirring at room temperature the MeOH evaporated under reduced pressure and the remaining oil was redissolved in anhydrous DMF (3 ml). Methanesulfonic acid 4-(2-methanesulfonyloxy-ethyl)-phenyl ester (1.00 g, 3.39 mmol), dissolved in anhydrous DMF (2 mL) was added dropwise and the reaction was stirred at room temperature for 4 h. Additional thioacetic acid (0.14 g, 1.86 mmol) was added to the reaction mixture. After 30 min. stirring, the mixture was partioned between EtOAc and brine. The separated organic layer was dried (Na2SO4) and finally concentration under reduced pressure. The crude material was purified by flash chromatography on silica gel 60 using n-heptan/EtOAc 7:3 as the eluent to afford the title compound as an oil. 1H NMR (400 MHz, CDCl3): δ 7.17-7.25 (m, 4H), 3.10 (s, 3H), 3.05-3.08 (t, 2H), 2.83-2.86 (t, 2H), 2.30 (s, 3H).

Workup

  1. customevaporated under reduced pressure
  2. dissolutionthe remaining oil was redissolved in anhydrous DMF (3 ml)
  3. additionwas added dropwise
  4. stirringAfter 30 min. stirring
  5. customThe separated organic layer was dried
  6. concentration(Na2SO4) and finally concentration under reduced pressure
  7. customThe crude material was purified by flash chromatography on silica gel 60 using n-heptan/EtOAc 7:3 as the eluent

Sources & evidence

ORD record
ord-1d3135f0ac914551bda2237c4b896668
Source dataset
uspto-grants-2015_11
Patent number
US09181181B2

Reaction notes

Loading…