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

HRID 611801Notes

Reaction equation

HRID 611801 reaction equation
[CH2:1](I)[CH2:2][CH3:3].C([O:8][C@@H:9]1[C@@H:14]([O:15][C:16](=O)[CH3:17])[C@H:13]([CH3:19])[O:12][CH:11]=[CH:10]1)(=O)C.[OH-].[Na+].[CH3:22]S(C)=O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC>[CH2:1]([O:8][C@@H:9]1[C@@H:14]([O:15][CH2:16][CH2:17][CH3:22])[C@H:13]([CH3:19])[O:12][CH:11]=[CH:10]1)[CH2:2][CH3:3]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 14798Sodium HydroxideHCID 336431-IodopropaneHCID 2734733L-arabino-Hex-1-enitol, 1,5-anhydro-2,6-dideoxy-, diacetate

Product 1

HCID 183962703,4-Di-O-n-propyl-6-deoxy-L-glucalYield 94%

Reagents, catalysts & solvents 1

HCID 94433Tetrabutylammonium hydrogen sulfateCatalyst

Procedure

n-Propyl iodide (39 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. The mixture was stirred for 17 h. at room temperature. The mixture was partitioned between water and pentane. The aqueous layer was extracted with additional pentane. The combined organic layers were successively washed with water (three times), dilute aqueous sodium thiosulfate, dilute sodium bicarbonate and brine. The solvent was removed under reduced pressure (20 Torr followed by 0.1 Torr) to yield a pale yellow oil (4.0 g, 94%) that could be used without further purification. 1H NMR d 6.31 (dd, J=6.1, 1.4, 1 H), 4.78 (dd, J=6.1, 2.4, 1 H), 1.60 (m, 4 H), 1.37 (d, J=6.4, 3 H), 0.93 (t, J=6.3, 3 H), 0.94 (t, J=6.3, 3 H).

Workup

  1. customthree-neck flask equipped with an overhead stirrer
  2. stirringThe mixture was stirred for 17 h. at room temperature
  3. customThe mixture was partitioned between water and pentane
  4. extractionThe aqueous layer was extracted with additional pentane
  5. washThe combined organic layers were successively washed with water (three times), dilute aqueous sodium thiosulfate, dilute sodium bicarbonate and brine
  6. customThe solvent was removed under reduced pressure (20 Torr followed by 0.1 Torr)

Sources & evidence

ORD record
ord-a29df110581d42ba8fcbcab20801f2db
Source dataset
uspto-grants-1999_12
Patent number
US06001981

Reaction notes

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