Potassium Carbonate → 1-acetyl-4-[(4-isopropoxyphenyl)-methyl]-5-methyl-3-(2,3,4,6-tetra-O-pivaloyl-beta-D-glucopyranosyloxy)-1H-pyrazole

HRID 910589Notes

Reaction equation

HRID 910589 reaction equation
[C:1]([N:4]1[C:8]([CH3:9])=[C:7]([CH2:10][C:11]2[CH:16]=[CH:15][C:14]([O:17][CH:18]([CH3:20])[CH3:19])=[CH:13][CH:12]=2)[C:6](=[O:21])[NH:5]1)(=[O:3])[CH3:2].C(=O)([O-])[O-].[K+].[K+].[C:28]([O:34][C@@H:35]1[C@@H:40]([O:41][C:42](=[O:47])[C:43]([CH3:46])([CH3:45])[CH3:44])[C@H:39]([O:48][C:49](=[O:54])[C:50]([CH3:53])([CH3:52])[CH3:51])[C@@H:38]([CH2:55][O:56][C:57](=[O:62])[C:58]([CH3:61])([CH3:60])[CH3:59])[O:37][C@@H:36]1Br)(=[O:33])[C:29]([CH3:32])([CH3:31])[CH3:30]>C(#N)C.O1CCCC1>[C:1]([N:4]1[C:8]([CH3:9])=[C:7]([CH2:10][C:11]2[CH:12]=[CH:13][C:14]([O:17][CH:18]([CH3:19])[CH3:20])=[CH:15][CH:16]=2)[C:6]([O:21][C@@H:36]2[O:37][C@H:38]([CH2:55][O:56][C:57](=[O:62])[C:58]([CH3:61])([CH3:60])[CH3:59])[C@@H:39]([O:48][C:49](=[O:54])[C:50]([CH3:51])([CH3:52])[CH3:53])[C@H:40]([O:41][C:42](=[O:47])[C:43]([CH3:44])([CH3:45])[CH3:46])[C@H:35]2[O:34][C:28](=[O:33])[C:29]([CH3:32])([CH3:30])[CH3:31])=[N:5]1)(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 10886360((2R,3R,4S,5R,6R)-6-bromo-3,4,5-tris(2,2-dimethylpropanoyloxy)oxan-2-yl)methyl 2,2-dimethylpropanoateHCID 673496361-acetyl-5-methyl-4-{[4-(propan-2-yloxy)phenyl]methyl}-2,3-dihydro-1H-pyrazol-3-one

Product 1

HCID 673498631-acetyl-4-[(4-isopropoxyphenyl)-methyl]-5-methyl-3-(2,3,4,6-tetra-O-pivaloyl-beta-D-glucopyranosyloxy)-1H-pyrazoleYield 80.2%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of 1-acetyl-1,2-dihydro-4-[(4-isopropoxyphenyl)methyl]-5-methyl-3H-pyrazol-3-one (1.00 g) in acetonitrile (5 mL) and tetrahydrofuran (3 mL) was added potassium carbonate (0.719 g) under stirring at room temperature. After stirring the mixture at 50° C. for 1 hour, 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (2.35 g) was added to the mixture. The mixture was stirred at 50° C. for 12 hours. After the reaction completed, the insoluble materials were removed by filtration, and the filtrate was concentrated under reduced pressure. 2-Propanol was added to the residue, and the mixture was re-concentrated under reduced pressure. The residue was recrystallized in the mixed solvent of water and methanol, the obtained crystals were dried under reduced pressure to give 1-acetyl-4-[(4-isopropoxyphenyl)methyl]-5-methyl-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-1H-pyrazole (2.19 g).

Workup

  1. stirringAfter stirring the mixture at 50° C. for 1 hour
  2. stirringThe mixture was stirred at 50° C. for 12 hours
  3. customthe insoluble materials were removed by filtration
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. addition2-Propanol was added to the residue
  6. concentrationthe mixture was re-concentrated under reduced pressure
  7. customThe residue was recrystallized in the mixed solvent of water and methanol
  8. customthe obtained crystals were dried under reduced pressure

Sources & evidence

ORD record
ord-b6aa6092894b4acdaa8f85311657e243
Source dataset
uspto-grants-2011_09
Patent number
US08022192B2

Reaction notes

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