Cesium carbonate → 4-[(4-ethylphenyl)methyl]-3-(beta-D-glucopyranosyloxy)-1-(3-hydroxypropyl)-5-methyl-1H-pyrazole

HRID 457522Notes

Reaction equation

[CH2:1]([C:3]1[CH:8]=[CH:7][C:6]([CH2:9][C:10]2[C:11]([O:16][C@@H:17]3[O:34][C@H:33]([CH2:35][O:36]C(=O)C)[C@@H:28]([O:29]C(=O)C)[C@H:23]([O:24]C(=O)C)[C@H:18]3[O:19]C(=O)C)=[N:12][NH:13][C:14]=2[CH3:15])=[CH:5][CH:4]=1)[CH3:2].C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:46]([O:53]CCCBr)[C:47]1C=CC=C[CH:48]=1.[OH-].[Na+]>C(#N)C.O.CO>[CH2:1]([C:3]1[CH:8]=[CH:7][C:6]([CH2:9][C:10]2[C:11]([O:16][C@@H:17]3[O:34][C@H:33]([CH2:35][OH:36])[C@@H:28]([OH:29])[C@H:23]([OH:24])[C@H:18]3[OH:19])=[N:12][N:13]([CH2:48][CH2:47][CH2:46][OH:53])[C:14]=2[CH3:15])=[CH:5][CH:4]=1)[CH3:2]

Participants

Conditions

Temperature: 80 °C

Procedure

To a suspension of 4-[(4-ethylphenyl)methyl]-5-methyl-3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-1H-pyrazole (0.030 g) and cesium carbonate (0.091 g) in acetonitrile (0.4 mL) was added benzyl(3-bromopropyl)ether (0.039 mL), and the mixture was stirred at 80° C. for 30 minutes. To the reaction mixture were added methanol (0.4 mL) and 2 mol/L aqueous sodium hydroxide solution (0.55 mL), and the mixture was stirred at room temperature overnight. Water was added to the reaction mixture, and the mixture was purified by solid phase extraction on ODS (washing solvent: distilled water, eluent: methanol). To the resulting eluent was added a catalytic amount of 10% palladium-carbon powder, and the mixture was stirred at room temperature under a hydrogen atmosphere for 3 days. Insoluble materials were removed by filtration, and the solvent of the filtrate was removed under reduced pressure. The residue was purified by liquid chromatography on ODS (eluent: methanol/water=40/60) to give 4-[(4-ethylphenyl)methyl]-3-(β-D-glucopyranosyloxy)-1-(3-hydroxypropyl)-5-methyl-1H-pyrazole (0.0080 g).

Workup

stirringthe mixture was stirred at room temperature overnight
distillationthe mixture was purified by solid phase extraction on ODS (washing solvent: distilled water, eluent: methanol)
additionTo the resulting eluent was added a catalytic amount of 10% palladium-carbon powder
stirringthe mixture was stirred at room temperature under a hydrogen atmosphere for 3 days
customInsoluble materials were removed by filtration
customthe solvent of the filtrate was removed under reduced pressure
customThe residue was purified by liquid chromatography on ODS (eluent: methanol/water=40/60)

Sources & evidence

ORD record: ord-047c03772cd8410989d1124ccf75f922
Source dataset: uspto-grants-2007_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07189702B2

Reaction notes

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