Dimethyl Sulfoxide → 3,4-Di-O-ethyl-6-deoxy-L-glucal

HRID 611800Notes

Reaction equation

HRID 611800 reaction equation
C(I)C.[C:4]([O:7][C@@H:8]1[C@@H:13]([O:14][C:15](=O)[CH3:16])[C@H:12]([CH3:18])[O:11][CH:10]=[CH:9]1)(=O)[CH3:5].[OH-].[Na+].CS(C)=O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC>[CH2:4]([O:7][C@@H:8]1[C@@H:13]([O:14][CH2:15][CH3:16])[C@H:12]([CH3:18])[O:11][CH:10]=[CH:9]1)[CH3:5]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 6340IodoethaneHCID 14798Sodium HydroxideHCID 2734733L-arabino-Hex-1-enitol, 1,5-anhydro-2,6-dideoxy-, diacetate

Product 1

HCID 183962683,4-Di-O-ethyl-6-deoxy-L-glucalYield 87%

Reagents, catalysts & solvents 1

HCID 94433Tetrabutylammonium hydrogen sulfateCatalyst

Procedure

Ethyl iodide (32 mL, 0.40 mol), 3,4-di-O-acetyl-6-deoxy-L-glucal (4.28 g, 0.20 mol), 50% aqueous NaOH (43 mL, 0.81 mol) and DMSO (11.4 mL, 0.16 mol) were added sequentially to a 300-mL round-bottom, three-neck flask equipped with an overhead stirrer. Stirring was begun and tetrabutylammonium hydrogen sulfate (2.04 g, 0.006 mol) added in a single portion. Stirring was continued for 66 h. The mixture was partitioned between water and Et2O. The aqueous layer was extracted twice with Et2O (20 mL) and a final time with 1:1 Et2O-CH2Cl2 (20 mL). The organic layers were combined, washed successively with water, dilute aqueous sodium thiosulfate, water and brine and dried over sodium sulfate and potassium carbonate and concentrated under reduced pressure. A white solid precipitated during evaporation. The mixture was diluted with pentane and the solid removed by filtration. The solvent was removed from the filtrate under reduced pressure to yield a pale yellow oil (3.2 g, 87%) which was sufficiently homogeneous to use in subsequent reactions without additional purification. 1H NMR d 6.32 (dd, J=6.1, 0.6, 1 H), 4.78 (dd, J=6.1, 1.2, 1 H), 1.36 (d, J=6.4, 3 H), 1.22 (t, J=7.0, 6 H).

Workup

  1. customthree-neck flask equipped with an overhead stirrer
  2. stirringStirring
  3. customThe mixture was partitioned between water and Et2O
  4. extractionThe aqueous layer was extracted twice with Et2O (20 mL)
  5. washwashed successively with water, dilute aqueous sodium thiosulfate, water and brine
  6. dry with materialdried over sodium sulfate and potassium carbonate
  7. concentrationconcentrated under reduced pressure
  8. customA white solid precipitated during evaporation
  9. additionThe mixture was diluted with pentane
  10. customthe solid removed by filtration
  11. customThe solvent was removed from the filtrate under reduced pressure

Sources & evidence

ORD record
ord-b2e5f16284884851ac25f6b2984b451d
Source dataset
uspto-grants-1999_12
Patent number
US06001981

Reaction notes

Loading…