5-[3-(Carboxymethyl)benzoyl]thieno[2,3-b]thiophene-2-carboxylic acid → HCID 20377676, compound

HRID 2052354Notes

Reaction equation

HRID 2052354 reaction equation
C([C:4]1[S:8][C:7]2[S:9][C:10]([C:12]([C:14]3[CH:15]=[C:16]([CH2:20][C:21]([OH:23])=[O:22])[CH:17]=[CH:18][CH:19]=3)=[O:13])=[CH:11][C:6]=2[CH:5]=1)(O)=O>[Cu]>[S:9]1[C:7]2[S:8][CH:4]=[CH:5][C:6]=2[CH:11]=[C:10]1[C:12]([C:14]1[CH:15]=[C:16]([CH2:20][C:21]([OH:23])=[O:22])[CH:17]=[CH:18][CH:19]=1)=[O:13]

Participants

3

Reactant 1

HCID 203776805-[3-(Carboxymethyl)benzoyl]thieno[2,3-b]thiophene-2-carboxylic acid

Product 1

HCID 20377676HCID 20377676, compoundYield 50.6%

Reagents, catalysts & solvents 1

HCID 23978CopperCatalyst

Conditions

Temperature
290 °C

Procedure

A homogeneous mixture of 3-(5-carboxythieno[2,3-b]thien-2-yl)carbonyl-phenylacetic acid (24 g), copper powder (4 g) and Fontainebleau sand (100 g) is heated at 290° C. for 1 hour. After cooling, the reaction mixture is washed five times with methylene chloride (total 350 cc). The combined methylene chloride phases are extracted five times with a 10% (w/v) aqueous solution of sodium carbonate (total 400 cc). The combined alkaline liquors are stirred with decolourizing charcoal (1 g), filtered, acidified to pH 1 by addition of 12 N concentrated aqueous solution of hydrogen chloride, and extracted three times with methylene chloride (total 300 cc). The combined methylene chloride solutions are dried over anhydrous sodium sulphate and evaporated. The residue (17.3 g) is dissolved in boiling acetonitrile (50 cc) and the solution is filtered. After cooling for 1 hour at 4° C., the resulting crystals are filtered off, washed three times with iced acetonitrile (total 15 cc) and dried under reduced pressure (20 mm Hg) at a temperature of about 20° C., in the presence of potassium hydroxide pellets used as a dehydrating agent. Crude 3-(thieno[2,3-b]thien-2-yl)carbonyl-phenylacetic acid (10.6 g), melting at 121° C., is thus obtained.

Workup

  1. temperatureAfter cooling
  2. washthe reaction mixture is washed five times with methylene chloride (total 350 cc)
  3. extractionThe combined methylene chloride phases are extracted five times with a 10% (w/v) aqueous solution of sodium carbonate (total 400 cc)
  4. filtrationfiltered
  5. additionacidified to pH 1 by addition of 12 N concentrated aqueous solution of hydrogen chloride
  6. extractionextracted three times with methylene chloride (total 300 cc)
  7. dry with materialThe combined methylene chloride solutions are dried over anhydrous sodium sulphate
  8. customevaporated
  9. dissolutionThe residue (17.3 g) is dissolved
  10. filtrationthe solution is filtered
  11. temperatureAfter cooling for 1 hour at 4° C.
  12. filtrationthe resulting crystals are filtered off
  13. washwashed three times with iced acetonitrile (total 15 cc)
  14. dry with materialdried under reduced pressure (20 mm Hg) at a temperature of about 20° C., in the presence of potassium hydroxide pellets

Sources & evidence

ORD record
ord-9b8fddd191884c499fa523e7e9472722
Source dataset
uspto-grants-1980_01
Patent number
US04183944

Reaction notes

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