alpha-D-Glucopyranosyl bromide, tetraacetate → HCID 18651720, compound

HRID 248322Notes

Reaction equation

HRID 248322 reaction equation
[CH3:1]/[C:2](=[CH:5]\[CH2:6][N:7]1[C:11](=[O:12])[C:10]2=[CH:13][CH:14]=[CH:15][CH:16]=[C:9]2[C:8]1=[O:17])/[CH2:3][OH:4].[C:18]([O:21][C@@H:22]1[C@@H:27]([O:28][C:29](=[O:31])[CH3:30])[C@H:26]([O:32][C:33](=[O:35])[CH3:34])[C@@H:25]([CH2:36][O:37][C:38](=[O:40])[CH3:39])[O:24][C@@H:23]1Br)(=[O:20])[CH3:19]>C1(C)C=CC=CC=1>[C:18]([O:21][C@@H:22]1[C@@H:27]([O:28][C:29](=[O:31])[CH3:30])[C@H:26]([O:32][C:33](=[O:35])[CH3:34])[C@@H:25]([CH2:36][O:37][C:38](=[O:40])[CH3:39])[O:24][C@H:23]1[O:4][CH2:3]/[C:2](/[CH3:1])=[CH:5]/[CH2:6][N:7]1[C:8](=[O:17])[C:9]2=[CH:16][CH:15]=[CH:14][CH:13]=[C:10]2[C:11]1=[O:12])(=[O:20])[CH3:19]

Participants

4

Reactant 2

HCID 101776alpha-D-Glucopyranosyl bromide, tetraacetateHCID 13323345HCID 13323345, compound

Product 1

HCID 18651720HCID 18651720, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

The general procedure of glucuronide formation of R. B. Conrow and S. Bernstein, 1971, supra, was followed. A mixture of 11 g (0.048 mol) of E-2-methyl-4-phthalimidobut-2-enol (mp 104°-105°, J. Corse and J. Kuhnle, Synthesis 618-619 (1972) and 17.2 g of CdCO3 (Johnson and Matthey, Seabrook, N. H.) in 1200 mL of toluene was dried by distilling about 200 mL of toluene from the flask (stirring). A solution of 39.7 g (0.1 mol) of 2,3,4,6-tetra-O-acetyl-α-glucopyranosyl bromide (acetobromoglucose) in 200 mL of dry toluene was added to the stirred, refluxing mixture over 1 h. The hot mixture was filtered through a Celite pad and the toluene was removed in vacuo from the filtrate. The resulting tan gum (46 g) contained the desired product, starting alcohol and its acetate. Purification was simplified by acetylating the entire mixture with 50 mL of acetic anhydride, 135 mL of pyridine and 1 g of 4-dimethylaminopyridine (steam bath, 1/2 h). The volatiles were removed in vacuo and the residue was dissolved in ethyl acetate and the solution washed with H2O, dilute HCl, KHCO3 solution and H2O. After drying and removal of the solvent, 29.8 g remained, which was divided into 4 portions and chromatographed on silica (J. T. Baker, flash chromatography grade, 40 μm, 50 cm×4 cm column, hexane:ethyl acetate (65:35); yield 14.36 g (53.3%); mp 118°-120°; 1H NMR identical to that reported by C. C. Duke et al., Australian Journal of Chemistry 31: 1291-1301 (1978).

Workup

  1. customwas dried
  2. distillationby distilling about 200 mL of toluene
  3. temperaturerefluxing mixture over 1 h
  4. filtrationThe hot mixture was filtered through a Celite pad
  5. customthe toluene was removed in vacuo from the filtrate
  6. customPurification
  7. customwith 50 mL of acetic anhydride, 135 mL of pyridine and 1 g of 4-dimethylaminopyridine (steam bath, 1/2 h)
  8. customThe volatiles were removed in vacuo
  9. dissolutionthe residue was dissolved in ethyl acetate
  10. washthe solution washed with H2O, dilute HCl, KHCO3 solution and H2O
  11. customAfter drying
  12. customremoval of the solvent, 29.8 g
  13. customchromatographed on silica (J

Sources & evidence

ORD record
ord-a102f54f12c0412a810cf916e4091c0f
Source dataset
uspto-grants-1993_05
Patent number
US05210077

Reaction notes

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