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Potassium Carbonate → 4-bromo-5-(1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylic Acid

HRID 1961011
Notes
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Reaction equation

HRID 1961011 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:8]([OH:10])=[O:9])[S:5][C:6]=1Br.C([O-])([O-])=O.[K+].[K+].CC1(C)COB([C:24]2[N:28]([CH3:29])[N:27]=[CH:26][CH:25]=2)OC1>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[CH:3]=[C:4]([C:8]([OH:10])=[O:9])[S:5][C:6]=1[C:24]1[N:28]([CH3:29])[N:27]=[CH:26][CH:25]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 806114,5-Dibromothenoic acidHCID 441194445-(5,5-Dimethyl-1,3,2-dioxaborinan-2-YL)-1-methyl-1H-pyrazole

Product 1

HCID 578265674-bromo-5-(1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylic Acid

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compound
Catalyst
HCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
80 °C

Procedure

To a solution of 4,5-dibromo-2-thiophenecarboxylic acid (1 g, 3.5 mmol) in dioxane/H2O (5:1, 18 mL) was added K2CO3 (1.9 g, 13.98 mmol), tetrakistriphenylphosphine Pd(0) (201 mg, 0.175 mmol) and 5-(5,5-dimethyl-1,3,2-dioxaborinane-2-yl)-1-methyl-1H-pyrazole (678 mg, 3.5 mmol). The reaction mixture was heated to 80° C. in a sealed tube for 12 h and was then partitioned between 6N NaOH and DCM. The pH of the aqueous phase was adjusted to ˜3 with 3M HCl and washed several times with DCM. The combined organic fractions were dried (Na2SO4), concentrated under vacuum and used directly without further purification (˜1 g, quant.): LC-MS (ES) m/z=288 (M+H)+.

Workup

  1. customwas then partitioned between 6N NaOH and DCM
  2. washwashed several times with DCM
  3. dry with materialThe combined organic fractions were dried (Na2SO4)
  4. concentrationconcentrated under vacuum
  5. customused directly without further purification (˜1 g, quant.)

Sources & evidence

ORD record
ord-747ad90030374cf19675dfd330013c84
Source dataset
uspto-grants-2013_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08410158B2

Reaction notes

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