Hydrochloric Acid → HCID 20377688, compound

HRID 2052358Notes

Reaction equation

HRID 2052358 reaction equation
C([C:4]1[S:8][C:7]2[S:9][C:10]([C:12]([C:14]3[CH:15]=[C:16]([CH:20]([CH2:24][CH3:25])[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.Cl.C(#N)C>N1C2C(=CC=CC=2)C=CC=1.[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]([CH:20]([CH2:24][CH3:25])[C:21]([OH:23])=[O:22])[CH:17]=[CH:18][CH:19]=1)=[O:13]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 6342AcetonitrileHCID 20377699HCID 20377699, compound

Product 1

HCID 20377688HCID 20377688, compoundYield 56.7%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 7047QuinolineSolvent

Procedure

2-{3-(5-Carboxy-thieno[2,3-b]thien-2-yl)carbonyl-phenyl}butyric acid (15.6 g) and copper powder (1 g) are suspended in quinoline (150 cc) and heated at 195°-200° C. for 20 minutes, and then at the boil for 10 minutes. After cooling, ice (300 g) and a 12 N concentrated aqueous solution of hydrogen chloride (100 cc) are added to the reaction mixture, which is extracted three times with methylene chloride (total 600 cc). The combined methylene chloride solutions are washed three times with distilled water (total 300 cc), and then extracted twice with a 2 N aqueous solution of sodium hydroxide (total 400 cc) and three times with distilled water (total 600 cc). The combined aqueous alkaline phases are acidified to pH 1 by the addition of a 12 N concentrated aqueous solution of hydrogen chloride and extracted three times with methylene chloride (total 450 cc). The combined methylene chloride solutions are washed three times with distilled water (total 300 cc), dried over anhydrous sodium sulphate in the presence of decolourizing charcoal (5 g), filtered and evaporated. The residue obtained (9.3 g) is dissolved in boiling acetonitrile (70 cc). After cooling, starting the crystallization and standing for one hour at 4° C., the resulting crystals are filtered off, washed once with iced acetonitrile (15 cc) and dried under reduced pressure (20 mm Hg) at a temperature of about 20° C., in the presence of potassium hydroxide pellets. Crude 2-{3-(thieno[2,3-b]thien-2-yl)carbonyl-phenyl}butyric acid (7.8 g), melting at 143° C., is thus obtained.

Workup

  1. temperatureheated at 195°-200° C. for 20 minutes
  2. temperatureAfter cooling
  3. extractionis extracted three times with methylene chloride (total 600 cc)
  4. washThe combined methylene chloride solutions are washed three times with distilled water (total 300 cc)
  5. extractionextracted twice with a 2 N aqueous solution of sodium hydroxide (total 400 cc) and three times with distilled water (total 600 cc)
  6. additionThe combined aqueous alkaline phases are acidified to pH 1 by the addition of a 12 N concentrated aqueous solution of hydrogen chloride
  7. extractionextracted three times with methylene chloride (total 450 cc)
  8. washThe combined methylene chloride solutions are washed three times with distilled water (total 300 cc)
  9. dry with materialdried over anhydrous sodium sulphate in the presence of decolourizing charcoal (5 g)
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue obtained (9.3 g)
  13. dissolutionis dissolved
  14. temperatureAfter cooling
  15. customthe crystallization
  16. waitstanding for one hour at 4° C.
  17. filtrationthe resulting crystals are filtered off
  18. washwashed once with iced acetonitrile (15 cc)
  19. 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-a7f2aa34e0eb4bcc879d6e6cf13e5c6c
Source dataset
uspto-grants-1980_01
Patent number
US04183944

Reaction notes

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