Potassium Carbonate → methyl 4-(4-ethenyl-1-methyl-1H-pyrazol-5-yl)-5-methyl-2-thiophenecarboxylate

HRID 2392076Notes

Reaction equation

HRID 2392076 reaction equation
Br[C:2]1[CH:3]=[N:4][N:5]([CH3:17])[C:6]=1[C:7]1[CH:8]=[C:9]([C:13]([O:15][CH3:16])=[O:14])[S:10][C:11]=1[CH3:12].C(=O)([O-])[O-].[K+].[K+].O1CCO[CH2:26][CH2:25]1>O.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH:25]([C:2]1[CH:3]=[N:4][N:5]([CH3:17])[C:6]=1[C:7]1[CH:8]=[C:9]([C:13]([O:15][CH3:16])=[O:14])[S:10][C:11]=1[CH3:12])=[CH2:26]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 312751,4-DioxaneHCID 57826393methyl 4-(4-bromo-1-methyl-1H-pyrazol-5-yl)-5-methyl-2-thiophenecarboxylate

Product 1

HCID 57826593methyl 4-(4-ethenyl-1-methyl-1H-pyrazol-5-yl)-5-methyl-2-thiophenecarboxylateYield 81%

Reagents, catalysts & solvents 2

HCID 178418851HCID 178418851, compoundCatalystHCID 962WaterSolvent

Procedure

A solution of methyl 4-(4-bromo-1-methyl-1H-pyrazol-5-yl)-5-methyl-2-thiophenecarboxylate (200 mg, 0.64 mmol)[prepared in Example 99], potassium carbonate (438 mg, 3.17 mmol), bis(tri-t-butylphosphine)palladium(0) (324 mg, 0.64 mmol) and 2,4,6-trivinylcycloboroxane-pyridine complex (77 mg, 0.32 mmol) in 1,4-dioxane (5.3 ml) and H2O (1 ml) was stirred at 80° C. in a sealed tube for 12 h. The reaction contents were partitioned between H2O-DCM and the aqueous phase was washed several times with DCM. The combined organic fractions were dried over Na2SO4, concentrated and purified via column chromatography (10-50% EtOAc in hexanes) affording methyl 4-(4-ethenyl-1-methyl-1H-pyrazol-5-yl)-5-methyl-2-thiophenecarboxylate (135 mg, 0.515 mmol, 81% yield) as a yellow oil: LCMS (ES) m/z=250 (M+H)+.

Workup

  1. customThe reaction contents
  2. customwere partitioned between H2O-DCM
  3. washthe aqueous phase was washed several times with DCM
  4. dry with materialThe combined organic fractions were dried over Na2SO4
  5. concentrationconcentrated
  6. custompurified via column chromatography (10-50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-583c855d1161431e8fc7d75286d85909
Source dataset
uspto-grants-2012_09
Patent number
US08273782B2

Reaction notes

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