Sodium Carbonate → 4-(4-Bromo-3-methoxycarbonylmethyl-thiophen-2-yl)-benzoic acid

HRID 2373711Notes

Reaction equation

HRID 2373711 reaction equation
Br[C:2]1[S:3][CH:4]=[C:5]([Br:12])[C:6]=1[CH2:7][C:8]([O:10][CH3:11])=[O:9].[C:13]([C:16]1[CH:21]=[CH:20][C:19](B(O)O)=[CH:18][CH:17]=1)([OH:15])=[O:14].C([O-])([O-])=O.[Na+].[Na+]>CC#N.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:12][C:5]1[C:6]([CH2:7][C:8]([O:10][CH3:11])=[O:9])=[C:2]([C:19]2[CH:20]=[CH:21][C:16]([C:13]([OH:15])=[O:14])=[CH:17][CH:18]=2)[S:3][CH:4]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 3121834-Carboxyphenylboronic AcidHCID 86607173Methyl (2,4-dibromothien-3-yl)acetate

Product 1

HCID 692003654-(4-Bromo-3-methoxycarbonylmethyl-thiophen-2-yl)-benzoic acidYield 69.7%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6342AcetonitrileSolvent

Procedure

Pd(PPh3)4 (0.046 g, 0.4 mmol was added to a degassed solution of methyl (2,4-dibromothien-3-yl)acetate (2.51 g, 8 mmol) and 4-carboxybenzeneboronic acid (1.32 g, 8 mmol) in Na2CO3(40 mL, 0.4 M, 16 mmol) and CH3CN (40 mL). The mixture was heated to reflux overnight under argon for 16 h. The solution was filtered hot and the filtrate was concentrated to about half volume. The solution was extracted with CH2Cl2. The aqueous phase was acidified with concentrated HCl and the resulting solid was collected by vacuum filtration and washed with H2O to yield 4-(4-bromo-3-methoxycarbonylmethyl-thiophen-2-yl)-benzoic acid (1.98 g) which was used without further purification.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux overnight under argon for 16 h
  3. filtrationThe solution was filtered hot
  4. concentrationthe filtrate was concentrated to about half volume
  5. extractionThe solution was extracted with CH2Cl2
  6. filtrationthe resulting solid was collected by vacuum filtration
  7. washwashed with H2O

Sources & evidence

ORD record
ord-cef14ed9fd214193955c414a410e118e
Source dataset
uspto-grants-2008_12
Patent number
US07459567B2

Reaction notes

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