Ammonium Hydroxide → Thieno[2,3-b]quinoline-4-carboxylic acid, methyl ester

HRID 641138Notes

Reaction equation

HRID 641138 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[NH:8][C:7](=O)[C:6]=1[CH:16]=[CH2:17])=[O:4].BrBr.NC(N)=[S:22].[OH-].[NH4+]>C(Cl)(Cl)Cl.C(O)C>[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[N:8]=[C:7]2[S:22][CH:17]=[CH:16][C:6]=12)=[O:4]

Participants

7

Reactant 4

HCID 14923Ammonium HydroxideHCID 24408BromineHCID 2723790ThioureaHCID 12294102Methyl-2-oxo-3-vinyl-1,2-dihydroquinoline-4-carboxylate

Product 1

HCID 12294104Thieno[2,3-b]quinoline-4-carboxylic acid, methyl ester

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6212ChloroformSolvent2×

Procedure

To a mixture of 1.8 g (7.2 mmol) Methyl-2-oxo-3-vinyl-1,2-dihydroquinoline-4-carboxylate 5 in 40 mL chloroform was added slowly over a dropping funnel a solution of 1.15 g (7.2 mmol) bromine in 40 mL chloroform and the reaction mixture was stirred for 1 hour at ambient temperature. After evaporation of the solvent the residue was mixed with 40 mL ethanol and 1.7 g (18 mmol) thiourea and refluxed for 2.5 h. After cooling the mixture was poured on ice, the pH-value was adjusted with ammonium hydroxide at pH=7-8 and the solution was extracted with 100 mL chloroform. The organic layer was separated, dried over sodium sulfate and filtered. Then the solvent was removed under reduced pressure and the crude product was purified by column chromatography on silica gel, eluting with methylene chloride/acetone 9:1, to give 1.0 of the desired product 14.

Workup

  1. customAfter evaporation of the solvent the residue
  2. temperaturerefluxed for 2.5 h
  3. temperatureAfter cooling the mixture
  4. additionwas poured on ice
  5. extractionthe solution was extracted with 100 mL chloroform
  6. customThe organic layer was separated
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. customThen the solvent was removed under reduced pressure
  10. customthe crude product was purified by column chromatography on silica gel
  11. washeluting with methylene chloride/acetone 9:1

Sources & evidence

ORD record
ord-666ecfeb51554126a4cd2eb4e9cc97dd
Source dataset
uspto-grants-2010_04
Patent number
US07695980B2

Reaction notes

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