Acetic Acid → 2,3,4,6-tetra-O-acetyl-5-thio-glucopyranose

HRID 2219463Notes

Reaction equation

HRID 2219463 reaction equation
C([O:4][CH:5]1[S:22][C@H:21]([CH2:23][O:24][C:25](=[O:27])[CH3:26])[C@@H:16]([O:17][C:18](=[O:20])[CH3:19])[C@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:6]1[O:7][C:8](=[O:10])[CH3:9])(=O)C.CNN.C(O)(=O)C.Cl>CN(C)C=O>[C:8]([O:7][C@@H:6]1[C@@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:16]([O:17][C:18](=[O:20])[CH3:19])[C@@H:21]([CH2:23][O:24][C:25](=[O:27])[CH3:26])[S:22][CH:5]1[OH:4])(=[O:10])[CH3:9]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 6061MethylhydrazineHCID 11654362(3R,4S,5S,6R)-6-(Acetoxymethyl)tetrahydro-2H-thiopyran-2,3,4,5-tetrayl tetraacetate

Product 1

HCID 116462702,3,4,6-tetra-O-acetyl-5-thio-glucopyranoseYield 88.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a solution of 1,2,3,4,6-penta-O-acetyl-5-thio-D-glucopyranose (34.0 g, 0.0837 mol) in N,N-dimethylformamide (300 mL), a mixture of methylhydrazine (6.70 mL, 0.120 mmol), acetic acid (15 mL, 0.120 mmol) and N,N-dimethylformamide (10 mL) was added in ice. After stirring at room temperature for 2.5 hours, 0.5M HCl (300 mL) was added to the reaction mixture in ice, which was then extracted twice with ethyl acetate (250 mL). The combined organic phases were washed sequentially with water (200 mL), saturated aqueous NaHCO3 (100 mL), water (100 mL) and saturated aqueous sodium chloride (100 mL), followed by addition of MgSO4 and activated charcoal (1 g). After filtration to remove the insoluble materials, the filtrate was concentrated under reduced pressure. The resulting residue was crystallized from isopropyl ether (70 mL) to give 2,3,4,6-tetra-O-acetyl-5-thio-glucopyranose (26.9 g, 88%) as a colorless crystal.

Workup

  1. additionwas added in ice
  2. extractionwhich was then extracted twice with ethyl acetate (250 mL)
  3. washThe combined organic phases were washed sequentially with water (200 mL), saturated aqueous NaHCO3 (100 mL), water (100 mL) and saturated aqueous sodium chloride (100 mL)
  4. additionfollowed by addition of MgSO4 and activated charcoal (1 g)
  5. filtrationAfter filtration
  6. customto remove the insoluble materials
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe resulting residue was crystallized from isopropyl ether (70 mL)

Sources & evidence

ORD record
ord-0d9f23eba8534c218c6242e9f62dd573
Source dataset
uspto-grants-2008_08
Patent number
US07414072B2

Reaction notes

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