Sodium hydride → 4-(4-But-2-ynyloxy-phenylsulfanylmethyl)-tetrahydro-pyran-4-carboxylic acid

HRID 278316Notes

Reaction equation

HRID 278316 reaction equation
[H-].[Na+].[CH2:3]([O:7][C:8]1[CH:13]=[CH:12][C:11]([SH:14])=[CH:10][CH:9]=1)[C:4]#[C:5][CH3:6].[C:15]1(=[O:24])[C:18]2([CH2:23][CH2:22][O:21][CH2:20][CH2:19]2)[CH2:17][O:16]1>C1COCC1>[CH2:3]([O:7][C:8]1[CH:9]=[CH:10][C:11]([S:14][CH2:17][C:18]2([C:15]([OH:24])=[O:16])[CH2:23][CH2:22][O:21][CH2:20][CH2:19]2)=[CH:12][CH:13]=1)[C:4]#[C:5][CH3:6]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 155411872,7-Dioxaspiro[3.5]nonan-1-oneHCID 235138844-But-2-ynyloxy-benzenethiol

Product 1

HCID 235138474-(4-But-2-ynyloxy-phenylsulfanylmethyl)-tetrahydro-pyran-4-carboxylic acidYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 0.112 g (2.81 mmol) of 60% sodium hydride in 2 mL of THF, cooled to 0° C., was added a solution of 0.500 g (2.81 mmol) of 4-but-2-ynyloxy-benzenethiol, dissolved in 3 mL of THF. The resulting mixture was stirred for 0.5 h at room temperature, then cooled to 5° C., followed by the addition of 0.518 g (3.65 on mol) of neat 2,7-dioxaspiro[3,5]nonane-1-one while keeping the reaction temperature below 10° C. The reaction was allowed to warm to room temperature and stirred for an additional 0.5 h and then quenched with 3 mL of 3N HCl solution and 3 mL of water. The resulting mixture was extracted with dichloromethane and the combined organics were washed with water and brine, dried over Na2SO4, filtered through a plug of silica gel and concentrated in vacuo. The residue was triturated with hexanes and acetonitrile and filtered to give 0.72 g of the carboxylic acid as a semi-solid. Electrospray Mass Spec: 319 (M−H)−

Workup

  1. temperaturecooled to 5° C.
  2. customthe reaction temperature below 10° C
  3. temperatureto warm to room temperature
  4. stirringstirred for an additional 0.5 h
  5. customquenched with 3 mL of 3N HCl solution and 3 mL of water
  6. extractionThe resulting mixture was extracted with dichloromethane
  7. washthe combined organics were washed with water and brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered through a plug of silica gel
  10. concentrationconcentrated in vacuo
  11. customThe residue was triturated with hexanes and acetonitrile
  12. filtrationfiltered

Sources & evidence

ORD record
ord-287b843f0d49477a859f9dbe3516e1ff
Source dataset
uspto-grants-2002_03
Patent number
US06358980B1

Reaction notes

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