Phosphoric Acid → Diacetone-D-glucose

HRID 2163419Notes

Reaction equation

HRID 2163419 reaction equation
[O:1]=[CH:2][C@@H:3]([C@H:5]([C@@H:7]([C@@H:9]([CH2:11][OH:12])[OH:10])[OH:8])[OH:6])[OH:4].OP(O)(O)=O>[Cl-].[Zn+2].[Cl-].S([O-])([O-])(=O)=O.[Cu+2].CC(C)=O>[CH3:2][C:3]1([CH3:5])[O:4][C@@H:3]([C@H:5]2[O:6][C@@H:11]3[O:12][C:9]([CH3:11])([CH3:7])[O:10][C@@H:9]3[C@H:7]2[OH:8])[CH2:2][O:1]1

Participants

6

Reactant 2

HCID 1004Phosphoric AcidHCID 107526(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal

Product 1

HCID 7067560Diacetone-D-glucose

Reagents, catalysts & solvents 3

HCID 24462Copper SulfateCatalystHCID 3007855ZincchlorideCatalystHCID 180AcetoneSolvent

Procedure

Anhydrous D-glucose (600w), dry acetone (4000v), anhydrous pulverized zinc chloride (480w) and 89% O-phosphoric acid (30v) and anhydrous copper sulphate (100w) were mechanically stirred for 30 hours at room temperature. Undissolved glucose was filtered and washed with acetone. The filtrate was cooled to 0°-5° C., made alkaline with sodium hydroxide (340w in 340w water) and filtered. The filtrate was evaporated under reduced pressure to remove solvent, the residue diluted with water and extracted with chloroform. The combined chloroform extract was washed with water, concentrated, dried and evaporated to give crude product (462w, 91% on recovered glucose), white crystals, mp 95°-101° C. Recrystallization from hexane/chloroform (2;1) afforded 1,2: 5,6-di-O-isopropylidene-α-D-glucofuranose, mp 105°-109° C.

Workup

  1. filtrationUndissolved glucose was filtered
  2. washwashed with acetone
  3. temperatureThe filtrate was cooled to 0°-5° C.
  4. filtrationfiltered
  5. customThe filtrate was evaporated under reduced pressure
  6. customto remove solvent
  7. additionthe residue diluted with water
  8. extractionextracted with chloroform
  9. extractionThe combined chloroform extract
  10. washwas washed with water
  11. concentrationconcentrated
  12. customdried
  13. customevaporated
  14. customto give crude product (462w, 91% on recovered glucose), white crystals, mp 95°-101° C
  15. customRecrystallization from hexane/chloroform (2;1)

Sources & evidence

ORD record
ord-2c524b2678ec4103bbc65c319905bd20
Source dataset
uspto-grants-1979_01
Patent number
US04133948

Reaction notes

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