Hydrochloric Acid → 1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-3-vinylcarbonyl-1H-pyrazole

HRID 253058Notes

Reaction equation

HRID 253058 reaction equation
[C:1]([C:4]1[C:8]([O:9][CH3:10])=[C:7]([C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)[N:6]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=2[Cl:24])[N:5]=1)([OH:3])=O.C[Li].[CH:27]([Mg]Br)=[CH2:28].Cl>O1CCCC1.O>[Cl:24][C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=1[N:6]1[C:7]([C:11]2[CH:12]=[CH:13][C:14]([Cl:17])=[CH:15][CH:16]=2)=[C:8]([O:9][CH3:10])[C:4]([C:1]([CH:27]=[CH2:28])=[O:3])=[N:5]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 668627343-carboxy-1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-1H-pyrazoleHCID 178418348HCID 178418348, compoundHCID 178418507HCID 178418507, compound

Product 1

HCID 668633311-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-3-vinylcarbonyl-1H-pyrazoleYield 70%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3-carboxy-1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-1H-pyrazole (1.09 g) in tetrahydrofuran (30 mL) was added dropwise methyl lithium (2.9 mL, 1.04 M diethylether solution) at −78° C. under nitrogen-gas atmosphere and the mixture was stirred at the same temperature for 30 minutes After warming to room temperature, to the reaction mixture was added dropwise vinylmagnesium bromide (7.7 mL, 0.97 M tetrahydrofuran solution) and the mixture was stirred at room temperature for 3 hours. To the reaction mixture was added water and an aqueous 1N HCl solution. After stirring, the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and filtered. The filtrate was concentrated in vacuo and the resultant crude product was purified by column chromatography on silica gel (solvent: hexane/ethyl acetate=90/10 to 85/15) to obtain 1-(2-chlorophenyl)-5-(4-chlorophenyl)-4-methoxy-3-vinylcarbonyl-1H-pyrazole (780 mg, yield: 70%) as a colorless solid.

Workup

  1. stirringthe mixture was stirred at room temperature for 3 hours
  2. stirringAfter stirring
  3. extractionthe mixture was extracted with ethyl acetate
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated in vacuo
  7. customthe resultant crude product was purified by column chromatography on silica gel (solvent: hexane/ethyl acetate=90/10 to 85/15)

Sources & evidence

ORD record
ord-9059f67a16c241ac9649c2335e20ab73
Source dataset
uspto-grants-2011_01
Patent number
US07872006B2

Reaction notes

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