Thieno(3,2-b)thiophene → HCID 20377679, compound

HRID 2052365Notes

Reaction equation

HRID 2052365 reaction equation
[S:1]1[CH:5]=[CH:4][C:3]2[S:6][CH:7]=[CH:8][C:2]1=2.Cl[C:10]([C:12]1[CH:13]=[C:14]([CH:18]([CH3:21])[C:19]#[N:20])[CH:15]=[CH:16][CH:17]=1)=[O:11].[Cl-].[Al+3].[Cl-].[Cl-]>C(Cl)Cl>[S:1]1[C:5]([C:10]([C:12]2[CH:13]=[C:14]([CH:18]([CH3:21])[C:19]#[N:20])[CH:15]=[CH:16][CH:17]=2)=[O:11])=[CH:4][C:3]2[S:6][CH:7]=[CH:8][C:2]1=2

Participants

5

Reactant 3

HCID 136063Thieno(3,2-b)thiopheneHCID 30163933-(1-Cyanoethyl)benzoyl chlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 20377679HCID 20377679, compoundYield 61.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

A solution of thieno[3,2-b]thiophene (28 g) and 2-(3-chloroformyl-phenyl)propionitrile (56.5 g) in methylene chloride (500 cc) is added dropwise, over a period of 1 hour, to a suspension of anhydrous aluminium chloride (83.5 g) in methylene chloride (500 cc). The mixture is stirred for 17 hours at a temperature of about 20° C. and then poured onto crushed ice (1 kg). The methylene chloride solution is decanted off, washed twice with distilled water (total 600 cc), twice with a 10% (w/v) aqueous sodium carbonate solution (total 600 cc), twice with distilled water (total 600 cc), dried over anhydrous sodium sulphate and evaporated. The residue is taken up in diethyl ether (600 cc), stirred with decolourizing charcoal (5 g) and filtered. The filtrate is evaporated and the residue (60 g), dissolved in methylene chloride (200 cc), is stirred for 2 hours with an N aqueous sodium hydroxide solution. The methylene chloride phase is decanted off, washed three times with distilled water (total 300 cc), dried over anhydrous sodium sulphate and evaporated. The residue (49 g) is dissolved in a boiling mixture of ethyl acetate (40 cc) and ethanol (160 cc). After cooling for 3 hours at 4° C., the resulting crystals are filtered off, washed twice with a mixture (total 40 cc) of ethyl acetate and ethanol (20:80) and dried under reduced pressure (20 mm Hg) at a temperature of about 20° C. in the presence of potassium hydroxide pellets. 2-{3-(Thieno[3,2-b]thien-2-yl)carbonyl-phenyl}propionitrile (36.6 g), melting at 75° C., is thus obtained.

Workup

  1. additionpoured
  2. customThe methylene chloride solution is decanted off
  3. washwashed twice with distilled water (total 600 cc), twice with a 10% (w/v) aqueous sodium carbonate solution (total 600 cc), twice with distilled water (total 600 cc)
  4. dry with materialdried over anhydrous sodium sulphate
  5. customevaporated
  6. stirringstirred with decolourizing charcoal (5 g)
  7. filtrationfiltered
  8. customThe filtrate is evaporated
  9. dissolutionthe residue (60 g), dissolved in methylene chloride (200 cc)
  10. stirringis stirred for 2 hours with an N aqueous sodium hydroxide solution
  11. customThe methylene chloride phase is decanted off
  12. washwashed three times with distilled water (total 300 cc)
  13. dry with materialdried over anhydrous sodium sulphate
  14. customevaporated
  15. dissolutionThe residue (49 g) is dissolved in a boiling mixture of ethyl acetate (40 cc) and ethanol (160 cc)
  16. temperatureAfter cooling for 3 hours at 4° C.
  17. filtrationthe resulting crystals are filtered off
  18. washwashed twice with a mixture (total 40 cc) of ethyl acetate and ethanol (20:80)
  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-714943c38f08450b97f1dd975efcd91c
Source dataset
uspto-grants-1980_01
Patent number
US04183944

Reaction notes

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