Allyl Alcohol → Tetrahydrothiopyran-4-one-3-carboxylic acid

HRID 841884Notes

Reaction equation

HRID 841884 reaction equation
[H-].[Na+].C(O)C=C.[S:7]([CH2:16][CH2:17][C:18]([O:20]CC=C)=[O:19])[CH2:8][CH2:9][C:10]([O:12]CC=C)=O>CCOCC>[S:7]1[CH2:8][CH2:9][C:10](=[O:12])[CH:17]([C:18]([OH:20])=[O:19])[CH2:16]1

Participants

5

Reactant 3

HCID 7858Allyl AlcoholHCID 24758Sodium hydrideHCID 14434560Diprop-2-en-1-yl 3,3'-sulfanediyldipropanoate

Product 1

HCID 22617731Tetrahydrothiopyran-4-one-3-carboxylic acidYield 83.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To a mixture of sodium hydride (60% in oil, 1.6 g, 38.7 mmol) in 10 mL of dry ether at room temperature was added allyl alcohol (2.25g, 38.7 mmol) in a dropwise manner. The resultant mixture was stirred for 15 min. A solution-of 3,3′-thiodipropionic acid, diallyl ester (5.0 g, 19.3 mmol) in 10 mL ether was slowly added and the mixture refluxed for 5 h. The reaction was cooled to room temperature and then quenched with water and the pH adjusted to 4 with IN HCl. The ether layer was separated and the aqueous layer was extracted with ether (2×100 mL). The combined etheral layer was washed with sautrated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was evaporated and the residue purified by flash column chromatography on silica gel eluted with hexane: ether (9 :1) to give 2.57 g of tetrahydrothiopyran-4-one-3-carboxylic acid, allyl ester.

Workup

  1. temperaturethe mixture refluxed for 5 h
  2. customquenched with water
  3. customThe ether layer was separated
  4. extractionthe aqueous layer was extracted with ether (2×100 mL)
  5. washThe combined etheral layer was washed with sautrated sodium chloride solution
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customThe solvent was evaporated
  8. customthe residue purified by flash column chromatography on silica gel
  9. washeluted with hexane: ether (9 :1)

Sources & evidence

ORD record
ord-c1c99658a38347b18cd9ba04b2146223
Source dataset
uspto-grants-2002_04
Patent number
US06372733B1

Reaction notes

Loading…