Tetrahydro-2H-pyran-4-yl 4-methylbenzenesulfonate → S-Tetrahydro-2H-pyran-4-YL ethanethioate

HRID 538626Notes

Reaction equation

HRID 538626 reaction equation
[O:1]1[CH2:6][CH2:5][CH:4](OS(C2C=CC(C)=CC=2)(=O)=O)[CH2:3][CH2:2]1.[C:18]([O-:21])(=[S:20])[CH3:19].[K+]>CN(C=O)C.[Na+].[I-]>[O:1]1[CH2:2][CH2:3][CH:4]([S:20][C:18](=[O:21])[CH3:19])[CH2:5][CH2:6]1

Participants

5

Reactant 2

HCID 13961807Tetrahydro-2H-pyran-4-yl 4-methylbenzenesulfonateHCID 23670855Potassium ethanethioate

Product 1

HCID 18533108S-Tetrahydro-2H-pyran-4-YL ethanethioateYield 81.3%

Reagents, catalysts & solvents 2

HCID 5238Sodium IodideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

To 300 g (1.175 mol) of toluene-4-sulfonic acid tetrahydropyran-4-yl ester in DMF (3 L) are added 268 g (2.35 mol) potassium thioacetate, followed by a catalytic amount of NaI (0.12 g, 10 mol %) at RT. After complete addition, the reaction is heated to 50° C. for 20 h. The reaction mixture is partitioned between TBME (3 L) and water (3 L), the aq. layer is extracted with TBME (2 L), then saturated with NaCl and extracted again with TBME (2×2 L). The combined organic extracts are dried over Na2SO4, filtered and the solvent is removed under reduced pressure to afford 153 g of thioacetic acid S-(tetrahydro-pyran-4-yl) ester. Yield: 81%; ESI-MS: 161 [M+H]+

Workup

  1. additionAfter complete addition
  2. customThe reaction mixture is partitioned between TBME (3 L) and water (3 L)
  3. extractionthe aq. layer is extracted with TBME (2 L)
  4. extractionsaturated with NaCl and extracted again with TBME (2×2 L)
  5. dry with materialThe combined organic extracts are dried over Na2SO4
  6. filtrationfiltered
  7. customthe solvent is removed under reduced pressure

Sources & evidence

ORD record
ord-b6c0326b5db24e7cb87ed512d00feaf8
Source dataset
uspto-grants-2014_10
Patent number
US08865744B1

Reaction notes

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