Cyanoacetic acid → HCID 69607335, compound

HRID 1244146Notes

Reaction equation

HRID 1244146 reaction equation
[C:1]([CH2:3][C:4](O)=[O:5])#[N:2].P(Cl)(Cl)(Cl)(Cl)Cl.[CH2:13]([O:15][C:16]([C:18]1[C:19]([C:24]2[S:25][C:26]([I:30])=[C:27]([CH3:29])[CH:28]=2)=[CH:20][S:21][C:22]=1[NH2:23])=[O:17])[CH3:14].C([O-])(O)=O.[Na+]>C(Cl)Cl>[CH2:13]([O:15][C:16]([C:18]1[C:19]([C:24]2[S:25][C:26]([I:30])=[C:27]([CH3:29])[CH:28]=2)=[CH:20][S:21][C:22]=1[NH:23][C:4](=[O:5])[CH2:3][C:1]#[N:2])=[O:17])[CH3:14]

Participants

6

Reactant 4

HCID 9740Cyanoacetic acidHCID 24819Phosphorus pentachlorideHCID 516892Sodium BicarbonateHCID 69607346HCID 69607346, compound

Product 1

HCID 69607335HCID 69607335, compoundYield 72.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Cyanoacetic acid (1.2 g, 14.0 mmol) and CH2Cl2 (14 ml) were combined at rt under N2. The solids do not dissolve. PCl5 (2.9 g, 14.0 mmol) was added as a solid portion wise (bubbles vigorously). The suspension was heated at reflux for 30 min and all solids dissolve to give a clear, light yellow solution. The acyl chloride solution was cooled and added directly to 5′-Amino-5-iodo-4-methyl-[2,3′]bithiophenyl-4′-carboxylic acid ethyl ester (2.0 g, 5.1 mmol) in CH2Cl2. The solution was stirred at rt for 2.5 h. The reaction was poured into NaHCO3 (aq, sat.) and washed a second time with NaHCO3 (aq, sat.). The organics were washed with brine and dried (Na2SO4), filtered and concentrated by rotary evaporation to give a light yellow solid which was then triturated with CH3CN and filtered to give 5′-(2-Cyano-acetylamino)-5-iodo-4-methyl-[2,3′]bithiophenyl-4′-carboxylic acid ethyl ester (1.7 g, 3.7 mmol) as a white solid. This material was taken to the next step without further purification.

Workup

  1. customwere combined at rt under N2
  2. dissolutionThe solids do not dissolve
  3. temperatureThe suspension was heated
  4. temperatureat reflux for 30 min
  5. dissolutionall solids dissolve
  6. customto give a clear, light yellow solution
  7. washwashed a second time with NaHCO3 (aq, sat.)
  8. washThe organics were washed with brine
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated by rotary evaporation
  12. customto give a light yellow solid which
  13. customwas then triturated with CH3CN
  14. filtrationfiltered

Sources & evidence

ORD record
ord-0a8f78a1c2804f489856460df3c7e3f7
Source dataset
uspto-grants-2006_10
Patent number
US07119205B2

Reaction notes

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