Acetic Acid → N-Benzhydryl-2,5-anhydro-2,5-imino-D-glucitol

HRID 486307Notes

Reaction equation

HRID 486307 reaction equation
[CH2:1]([OH:12])[C:2]([C@@H:4]([OH:11])[C@H:5]([OH:10])[C:6]([CH2:8][OH:9])=[O:7])=O.C([BH3-])#N.[Na+].[CH:17]([NH2:30])([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C(O)(=O)C>CO>[CH:17]([N:30]1[C@:2]2([CH2:1][OH:12])[O:7][C@:6]1([C@H:5]([C@@H:4]2[OH:11])[OH:10])[CH2:8][OH:9])([C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7036BenzhydrylamineHCID 995135-keto-D-Fructose2×HCID 5003444Sodium cyanoborohydride3×

Product 1

HCID 131718342N-Benzhydryl-2,5-anhydro-2,5-imino-D-glucitolYield 62.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A suspension of 5-keto-D-fructose (Formula X, 50 g, 0.28 mol; obtained from Chemical Dynamics) in 400 mL of MeOH was treated with sodium cyanoborohydride (40 g, 0.476 mol). A slurry of benzhydrylamine (42.0 mL, 0.234 mol) in 120-mL of MEOH was treated with sufficient acetic acid to bring the pH to 6-7 and then added over a 0.5 h period to the 5-keto-D-fructose (Formula X) and sodium cyanoborohydride suspension. An additional portion of sodium cyanoborohydride (20 g. 0.235 mol) was added and the mixture was stirred at reflux for 6 h. The solvent was then removed, and the residue treated with 10% sodium carbonate (ca. 100 mi), and the product was extracted into chloroform. The chloroform layers were dried (MgSO4), filtered and concentrated to give a tacky yellow solid. This was purified on two Waters Prep 500 columns (CHCl3 /MeOH/NH4OH, 88:11:1) to give ca. 50 g of the target compound. Recrystallization from ethyl acetate gave 21.3 g (28%) of white needles, 152.5°-154.5° C. (corrected). Both 1H and 13C NMR in CDCl3 supported the assigned structure.

Workup

  1. temperatureat reflux for 6 h
  2. customThe solvent was then removed
  3. additionthe residue treated with 10% sodium carbonate (ca. 100 mi)
  4. extractionthe product was extracted into chloroform
  5. dry with materialThe chloroform layers were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a tacky yellow solid
  9. customThis was purified on two Waters Prep 500 columns (CHCl3 /MeOH/NH4OH, 88:11:1)

Sources & evidence

ORD record
ord-e709c8a8dc354081ab01fb9916b1e758
Source dataset
uspto-grants-1994_03
Patent number
US05290948

Reaction notes

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