Sodium Hydroxide → 1-Isopropyl-4-(4-methoxybenzyl)-5-phenoxy-3-(beta-d-glucopyranosyloxy)-1h-pyrazole

HRID 2102265ノート

反応式

HRID 2102265 の反応式
[CH:1]([N:4]1[C:8]([O:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[C:7]([CH2:16][C:17]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=2)[C:6](=[O:25])[NH:5]1)([CH3:3])[CH3:2].CC([O:29][CH2:30][C@H:31]1[O:36][C@H:35](Br)[C@H:34]([O:38]C(C)=O)[C@@H:33]([O:42]C(C)=O)[C@@H:32]1[O:46]C(C)=O)=O.[OH-].[Na+]>ClCCl>[CH:1]([N:4]1[C:8]([O:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[C:7]([CH2:16][C:17]2[CH:18]=[CH:19][C:20]([O:23][CH3:24])=[CH:21][CH:22]=2)[C:6]([O:25][C@@H:35]2[O:36][C@H:31]([CH2:30][OH:29])[C@@H:32]([OH:46])[C@H:33]([OH:42])[C@H:34]2[OH:38])=[N:5]1)([CH3:2])[CH3:3]

参加物

5

反応物 3

HCID 14798Sodium HydroxideHCID 101776alpha-D-Glucopyranosyl bromide, tetraacetateHCID 231133691-Isopropyl-4-(4-methoxybenzyl)-5-phenoxy-1,2-dihydro-3H-pyrazol-3-one

生成物 1

HCID 113410021-Isopropyl-4-(4-methoxybenzyl)-5-phenoxy-3-(beta-d-glucopyranosyloxy)-1h-pyrazole収率 67.6%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a suspension of 1-isopropyl-4-(4-methoxybenzyl)-5-phenoxy-1,2-dihydro-3H-pyrazol-3-one (10 mg), acetobromo-α-D-glucose (40 mg) and benzyl(n-tributyl)ammonium chloride (30 mg) in dichloromethane (3 mL) was added sodium hydroxide aqueous solution (2 mol/L, 0.1 mL) and the mixture was stirred at room temperature for 2 hours. The reaction mixture was purified by column chromatography on aminopropylated silica gel (eluent: tetrahydrofuran). The obtained semi-purified 1-isopropyl-4-(4-methoxybenzyl)-5-phenoxy-3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy-1H-pyrazole was dissolved in methanol (5 mL) and sodium methoxide (28% methanol solution, 0.2 mL) was added to the solution. The mixture was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure and to the residue was added 10% citric acid aqueous solution. The mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure. The obtained residue was purified by preparative reverse phase column chromatography (Shiseido CAPSELLPAC C18 UG80, 5 μm, 20×50 mm, flowrate 30 mL/min linear gradient, water/methanol=70/30-10/90) to give 10 mg of the title compound.

後処理

  1. customThe reaction mixture was purified by column chromatography on aminopropylated silica gel (eluent: tetrahydrofuran)
  2. dissolutionThe obtained semi-purified 1-isopropyl-4-(4-methoxybenzyl)-5-phenoxy-3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy-1H-pyrazole was dissolved in methanol (5 mL)
  3. additionsodium methoxide (28% methanol solution, 0.2 mL) was added to the solution
  4. stirringThe mixture was stirred at room temperature for 2 hours
  5. concentrationThe reaction mixture was concentrated under reduced pressure and to the residue
  6. additionwas added 10% citric acid aqueous solution
  7. extractionThe mixture was extracted with ethyl acetate
  8. washThe organic layer was washed with brine
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customthe solvent was removed under reduced pressure
  11. customThe obtained residue was purified by preparative reverse phase column chromatography (Shiseido CAPSELLPAC C18 UG80, 5 μm, 20×50 mm, flowrate 30 mL/min linear gradient, water/methanol=70/30-10/90)

出典と根拠

ORDレコード
ord-1e80bcea51c64cfba419cdb35e16fc88
出典データセット
uspto-grants-2009_08
特許番号
US07576064B2

反応ノート

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