Acetic Acid → HCID 86587413, compound

HRID 1582858Notes

Reaction equation

HRID 1582858 reaction equation
C([O:4][C@@H:5]1[C@@H:10]([O:11]C(=O)C)[C@H:9]([O:15]C(=O)C)[C@@H:8]([CH2:19][O:20]C(=O)C)[O:7][C@@H:6]1Br)(=O)C.O[Li].O.[CH3:28][N:29]1[C@@H:45]2[CH2:46][C:34]3=[CH:35][CH:36]=[C:37]([OH:48])[C:38]4[O:39][C@H:40]5[C@@H:41]([OH:47])[CH2:42][CH2:43][C@@H:44]2[C@:32]5([C:33]=43)[CH2:31][CH2:30]1.C(O)(=O)C>CO.O.C(Cl)(Cl)Cl>[C@@H:6]1([O:48][C:37]2[CH2:36][CH2:35][C:34]3[CH2:46][C@H:45]4[N:29]([CH3:28])[CH2:30][CH2:31][C@:32]56[C:33]=3[C:38]=2[O:39][C@H:40]5[C@@H:41]([OH:47])[CH:42]=[CH:43][C@@H:44]46)[O:7][C@H:8]([CH2:19][OH:20])[C@@H:9]([OH:15])[C@H:10]([OH:11])[C@H:5]1[OH:4]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 101776alpha-D-Glucopyranosyl bromide, tetraacetateHCID 168937Lithium hydroxide, monohydrate2×HCID 5359421Dihydromorphine

Product 1

HCID 86587413HCID 86587413, compoundYield 30%

Reagents, catalysts & solvents 3

HCID 887MethanolSolvent2×HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl bromide (1.20 g, 3.0 mmol) was added in one portion to a stirred solution of LiOH·H2O (0.15 g, 3.5 mmol) and dihydromorphine (1.0 g, 3.0 mmol) in dry methanol (10 mL) at room temperature. The resulting mixture was stirred for 1 hr, a solution of LiOH·H2O (0.42 g, 10.0 mmol) in water (10 mL) was added dropwise to the mixture, and the mixture allowed to stir for an additional 3 hr. The resulting suspension was acidified to pH 7 with acetic acid (0.5 mL) and 20 mL of chloroform was added. The resulting precipitate was removed by filtration and washed with ethanol (20 mL) following by acetone (20 mL), to provide a crude product. The crude product was dissolved in 50% aqueous methanol (12 mL), recrystallized at 0° C., filtered, and dried under reduced pressure (10 mm Hg, 50° C.) to provide 0.33 g (30%) of 3-O—β-glucosyldihydromorphine.

Workup

  1. stirringto stir for an additional 3 hr
  2. additionwas added
  3. customThe resulting precipitate was removed by filtration
  4. washwashed with ethanol (20 mL)
  5. customto provide a crude product
  6. customrecrystallized at 0° C.
  7. filtrationfiltered
  8. customdried under reduced pressure (10 mm Hg, 50° C.)

Sources & evidence

ORD record
ord-fb52ed6be360422dbc1d459070adaae1
Source dataset
uspto-grants-2004_05
Patent number
US06740641B2

Reaction notes

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