Water → HCID 19990624, compound

HRID 346260Notes

Reaction equation

HRID 346260 reaction equation
[H-].[Na+].[CH2:3]([SH:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.C([O:14][CH2:15][CH:16]([CH2:21]Br)[C:17]([CH3:20])([CH3:19])[CH3:18])(=O)C.O>CN(C)C=O>[CH2:3]([S:10][CH2:21][CH:16]([C:17]([CH3:20])([CH3:19])[CH3:18])[CH2:15][OH:14])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 4

HCID 962WaterHCID 7509Benzyl mercaptanHCID 24758Sodium hydrideHCID 53800496HCID 53800496, compound

Product 1

HCID 19990624HCID 19990624, compoundYield 33.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

Sodium hydride (2 g; 80%) was added to a stirred solution of benzyl mercaptan (9.4 g) in dry dimethylformamide (100 ml) at room temperature under a nitrogen atmosphere. The resulting mixture was heated at reflux for 1 hour when a solution of 2-bromomethyl -3,3-dimethylbutyl acetate (13.3 g) in DMF (10 ml) was added. After a further hour at reflux, the mixture was allowed to cool and then poured into water (300 ml). The aqueous mixture was extracted with ether and then the combined ethereal extracts were washed with water before drying over anhydrous magnesium sulphate and evaporation in vacuo. The resulting residue was taken up in a mixture of 10% aqueous potassium hydroxide and ethanol (1:1, 50 ml) and heated to reflux for 1 hour. After cooling, the aqueous solution was exhaustively extracted with ether. The combined ethereal extracts were dried over anhydrous magnesium sulphate and then evaporated in vacuo. The residue was purified by column chromatography on silica. Gradient elution with hexane/diethylether mixtures gave 2-benzylthiomethyl-3,3-dimethylbutanol as an oil (4.5 g).

Workup

  1. temperatureThe resulting mixture was heated
  2. additionwas added
  3. temperatureAfter a further hour at reflux
  4. temperatureto cool
  5. extractionThe aqueous mixture was extracted with ether
  6. washthe combined ethereal extracts were washed with water
  7. dry with materialbefore drying over anhydrous magnesium sulphate and evaporation in vacuo
  8. additionThe resulting residue was taken up in a mixture of 10% aqueous potassium hydroxide and ethanol (1:1, 50 ml)
  9. temperatureheated
  10. temperatureto reflux for 1 hour
  11. temperatureAfter cooling
  12. extractionthe aqueous solution was exhaustively extracted with ether
  13. dry with materialThe combined ethereal extracts were dried over anhydrous magnesium sulphate
  14. customevaporated in vacuo
  15. customThe residue was purified by column chromatography on silica
  16. washGradient elution with hexane/diethylether mixtures

Sources & evidence

ORD record
ord-bd0c6f7bdace4f6f880c513ea83e5170
Source dataset
uspto-grants-1991_10
Patent number
US05061726

Reaction notes

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