Sodium Carbonate → 5-(3-Nitro-2-methoxy-5-methyl-phenyl)thiophene-2-carboxylic acid

HRID 384342Notes

Reaction equation

HRID 384342 reaction equation
[CH3:1][O:2][C:3]1[C:8]([N+:9]([O-:11])=[O:10])=[CH:7][C:6]([CH3:12])=[CH:5][C:4]=1B1OC(C)(C)C(C)(C)O1.Br[C:23]1[S:27][C:26]([C:28]([OH:30])=[O:29])=[CH:25][CH:24]=1.C(=O)([O-])[O-].[Na+].[Na+]>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>[N+:9]([C:8]1[C:3]([O:2][CH3:1])=[C:4]([C:23]2[S:27][C:26]([C:28]([OH:30])=[O:29])=[CH:25][CH:24]=2)[CH:5]=[C:6]([CH3:12])[CH:7]=1)([O-:11])=[O:10]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 3491155-Bromothiophene-2-carboxylic acidHCID 574838182-(2-Methoxy-5-methyl-3-nitrophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 574838195-(3-Nitro-2-methoxy-5-methyl-phenyl)thiophene-2-carboxylic acidYield 73.6%

Reagents, catalysts & solvents 3

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

Procedure

2-(2-Methoxy-5-methyl-3-nitro-phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 24a (4.0 g, 14.5 mmol), 5-bromothiophene-2-carboxylic acid (1.0 g, 4.8 mmol), tetrakis(triphenylphosphine)palladium (0.276 g, 0.24 mmol) and sodium carbonate (1.01 g, 9.6 mmol) were dissolved in 30 mL of 1,4-dioxane and 10 mL of water. The reaction mixture was heated to reflux for 1 hour. The reaction was monitored by TLC until the disappearance of the starting materials. The mixture was concentrated under reduced pressure and the residue was dissolved in water. The mixture was filtered to remove tetrakis(triphenylphosphine)palladium and the filtrate was extracted with ethyl acetate. The aqueous layer was acidified to form precipitates. The precipitates were dissolved in ethyl acetate, dried over anhydrous magnesium sulfate, filtered to remove the drying agent and concentrated under reduced pressure to obtain the title compound 5-(3-nitro-2-methoxy-5-methyl-phenyl)thiophene-2-carboxylic acid 24b (1.03 g, 73.6%) as a yellow solid.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 1 hour
  3. concentrationThe mixture was concentrated under reduced pressure
  4. dissolutionthe residue was dissolved in water
  5. filtrationThe mixture was filtered
  6. customto remove tetrakis(triphenylphosphine)palladium
  7. extractionthe filtrate was extracted with ethyl acetate
  8. customto form
  9. customprecipitates
  10. dissolutionThe precipitates were dissolved in ethyl acetate
  11. dry with materialdried over anhydrous magnesium sulfate
  12. filtrationfiltered
  13. customto remove the drying agent
  14. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-91f63d25192949b5be694a239b8310bc
Source dataset
uspto-grants-2013_02
Patent number
US08367710B2

Reaction notes

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