Sodium Carbonate → HCID 14551988, compound

HRID 2298347Notes

Reaction equation

HRID 2298347 reaction equation
Br[C:2]1[S:3][C:4]([Cl:7])=[CH:5][CH:6]=1.[CH:8]([C:10]1[S:14][C:13](B(O)O)=[CH:12][CH:11]=1)=[O:9].C([O-])([O-])=O.[Na+].[Na+]>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.CCO>[Cl:7][C:4]1[S:3][C:2]([C:13]2[S:14][C:10]([CH:8]=[O:9])=[CH:11][CH:12]=2)=[CH:6][CH:5]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 761332-Bromo-5-chlorothiopheneHCID 27734305-Formyl-2-thiopheneboronic acid

Product 1

HCID 14551988HCID 14551988, compoundYield 24%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolvent

Conditions

Temperature
85 °C

Procedure

In a flask are placed 2-bromo-5-chlorothiophene (0.55 mL, 5.0 mmol) and Pd(PPh3)4 (0.17 g, 0.15 mmol), and the flask is vacuum purged and nitrogen filled (3×). THF (10 mL) is added by syringe and stirred 10 min. In a separate flask is placed 5-formyl-2-thiopheneboronic acid (0.94 g, 6.0 mmol) and EtOH (2 mL) and stirred until dissolved. This mixture is added by syringe to the first flask followed by vacuum purge and nitrogen fill (3×). A solution of Na2CO3 (2M, 5.0 mL, 10.0 mmol) is added by syringe followed by vacuum purge and nitrogen fill (3×). The reaction mixture is heated at 85° C. for 20 h. The reaction is cooled to rt and diluted with water. The aqueous solution is extracted with ether (3×). The combined ether layers are washed with water (3×) then brine (2×). The ether is dried over MgSO4, filtered, and concentrated. The crude product is purified over silica gel (5% EtOAc-heptane) to provide the product as an orange solid (0.27 g, 24%). 1H NMR (400 MHz, CDCl3) δ 9.89, 7.69, 7.20, 7.16, 6.93.

Workup

  1. customIn a flask are placed
  2. custompurged
  3. additionnitrogen filled (3×)
  4. additionTHF (10 mL) is added by syringe
  5. customIn a separate flask is placed
  6. dissolutionuntil dissolved
  7. additionThis mixture is added by syringe to the first flask
  8. custompurge
  9. custompurge
  10. temperatureThe reaction is cooled to rt
  11. additiondiluted with water
  12. extractionThe aqueous solution is extracted with ether (3×)
  13. washThe combined ether layers are washed with water (3×)
  14. dry with materialThe ether is dried over MgSO4
  15. filtrationfiltered
  16. concentrationconcentrated
  17. customThe crude product is purified over silica gel (5% EtOAc-heptane)

Sources & evidence

ORD record
ord-a9f034f395264169ba4f452d9be4fabc
Source dataset
uspto-grants-2002_12
Patent number
US06492385B2

Reaction notes

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