Potassium Carbonate → methyl 4-bromo-3-hydroxy-5-(1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylate

HRID 1961008Notes

Reaction equation

HRID 1961008 reaction equation
[Br:1][C:2]1[C:3]([OH:12])=[C:4]([C:8]([O:10][CH3:11])=[O:9])[S:5][C:6]=1Br.CC1(C)COB([C:20]2[N:24]([CH3:25])[N:23]=[CH:22][CH:21]=2)OC1.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[C:3]([OH:12])=[C:4]([C:8]([O:10][CH3:11])=[O:9])[S:5][C:6]=1[C:20]1[N:24]([CH3:25])[N:23]=[CH:22][CH:21]=1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 2777613Methyl 4,5-dibromo-3-hydroxythiophene-2-carboxylateHCID 441194445-(5,5-Dimethyl-1,3,2-dioxaborinan-2-YL)-1-methyl-1H-pyrazole

Product 1

HCID 57826681methyl 4-bromo-3-hydroxy-5-(1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylateYield 15%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

Methyl 4,5-dibromo-3-hydroxy-2-thiophenecarboxylate (500 mg, 1.59 mmol), 5-(5,5-dimethyl-1,3,2-dioxaborinane-2-yl)-1-methyl-1H-pyrazole (339 mg, 1.75 mmol), Pd(PPh3)4 (92 mg, 79.4 μmol) and K2CO3 (876 mg, 6.35 mmol) in dioxane (6.6 mL) and H2O (1.3 mL) were combined in a sealed tube. After 12 h at 80° C., the reaction contents were partitioned between H2O/DCM. The aqueous phase was washed several times with DCM and the combined organic fractions were dried over Na2SO4, concentrated and purified via column chromatography (silica, 0.5% MeOH in DCM) affording the title compound (75 mg, 15%) as a brown residue: LCMS (ES) m/z=318 (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 (silica, 0.5% MeOH in DCM)

Sources & evidence

ORD record
ord-226cf4d272944e3d8ce16a7db29a6dee
Source dataset
uspto-grants-2013_04
Patent number
US08410158B2

Reaction notes

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