Dimethylformamide → methyl 3-[4-({4-[({4-[(Z)-2-(diethoxyphosphoryl)ethenyl]-1-phenyl-1H-pyrazol-3-yl}oxy)methyl]-2-methoxyphenoxy}methyl)-5-methyl-1,3-oxazol-2-yl]benzoate

HRID 2222001Notes

Reaction equation

HRID 2222001 reaction equation
C(C1CN([O:14][CH2:15][C:16]2[CH:39]=[CH:38][C:19]([O:20][CH2:21][C:22]3[N:23]=[C:24]([C:28]4[CH:29]=[C:30]([CH:35]=[CH:36][CH:37]=4)[C:31]([O:33][CH3:34])=[O:32])[O:25][C:26]=3[CH3:27])=[C:18]([O:40][CH3:41])[CH:17]=2)N(C2C=CC=CC=2)C=1)=O.[CH2:42]([P:51](=[O:58])([O:55][CH2:56][CH3:57])[O:52][CH2:53][CH3:54])P(=O)(OCC)OCC.[CH3:59][N:60]([CH3:63])C=O.[H-].[Na+]>O>[CH2:56]([O:55][P:51](/[CH:42]=[CH:27]\[C:26]1[C:22]([O:14][CH2:15][C:16]2[CH:39]=[CH:38][C:19]([O:20][CH2:21][C:22]3[N:23]=[C:24]([C:28]4[CH:29]=[C:30]([CH:35]=[CH:36][CH:37]=4)[C:31]([O:33][CH3:34])=[O:32])[O:25][C:26]=3[CH3:27])=[C:18]([O:40][CH3:41])[CH:17]=2)=[N:23][N:60]([C:63]2[CH:38]=[CH:39][CH:16]=[CH:17][CH:18]=2)[CH:59]=1)([O:52][CH2:53][CH3:54])=[O:58])[CH3:57]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 15455Tetraethyl methylenediphosphonateHCID 24758Sodium hydrideHCID 86605844methyl 3-{4-[(4-{[(4-formyl-1-phenyl-1H-pyrazol-2-yl)oxy]methyl)-2-methoxyphenoxy)methyl]-5-methyl-1,3-oxazol-2-yl}benzoate

Product 1

HCID 86605915methyl 3-[4-({4-[({4-[(Z)-2-(diethoxyphosphoryl)ethenyl]-1-phenyl-1H-pyrazol-3-yl}oxy)methyl]-2-methoxyphenoxy}methyl)-5-methyl-1,3-oxazol-2-yl]benzoateYield 4.4%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a mixture of methyl 3-{4-[(4-{[(4-formyl-1-phenyl-1H-pyrazol2-yl)oxy]methyl}-2-methoxyphenoxy)methyl]-5-methyl-1,3-oxazol-2-yl}benzoate (33.0 g), tetraethyl methylenediphosphonate (18.91 g) and N,N-dimethylformamide (300 mL) was added sodium hydride (60% in oil, 2.86 g) at 0° C., and the mixture was stirred at room temperature for 15 hrs. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give methyl 3-[4-({4-[({4-[(Z)-2-(diethoxyphosphoryl)ethenyl]-1-phenyl-1H-pyrazol-3-yl}oxy)methyl]-2-methoxyphenoxy}methyl)-5-methyl-1,3-oxazol-2-yl]benzoate as colorless crystals (1.82 g, yield 4.4%) from a fraction eluted with acetone-hexane (1:1, v/v). Recrystallization from ethyl acetate-hexane gave colorless prism crystals. melting point: 112-113° C.

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe organic layer was washed successively with water and saturated brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-3e4329a67f4f4f8eaa0f23442454f5b3
Source dataset
uspto-grants-2008_05
Patent number
US07368578B2

Reaction notes

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