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

HRID 7393Notes

Reaction equation

HRID 7393 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

8

Reactant 4

HCID 10796Cesium carbonateHCID 14798Sodium HydroxideHCID 2776064Benzyl 3-Bromopropyl EtherHCID 673355784-[(4-Ethylphenyl)methyl]-5-methyl-3-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyloxy)-1H-pyrazole

Product 1

HCID 690132554-[(4-ethylphenyl)methyl]-3-(beta-D-glucopyranosyloxy)-1-(3-hydroxypropyl)-5-methyl-1H-pyrazole

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6342AcetonitrileSolvent

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

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

Sources & evidence

ORD record
ord-b269f573691d4ca6aca44037f3491647
Source dataset
uspto-grants-2006_08
Patent number
US07087579B2

Reaction notes

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