Potassium Carbonate → Methyl 3-aminothieno[3,2-b]pyridine-2-carboxylate

HRID 57154Notes

Reaction equation

HRID 57154 reaction equation
Cl[C:2]1[C:3]([C:8]#[N:9])=[N:4][CH:5]=[CH:6][CH:7]=1.[C:10]([O:14][CH3:15])(=[O:13])[CH2:11][SH:12].C([O-])([O-])=O.[K+].[K+]>C(#N)C>[CH3:15][O:14][C:10]([C:11]1[S:12][C:2]2[C:3](=[N:4][CH:5]=[CH:6][CH:7]=2)[C:8]=1[NH2:9])=[O:13]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 16907Methyl ThioglycolateHCID 8182583-Chloropyridine-2-carbonitrile

Product 1

HCID 13793447Methyl 3-aminothieno[3,2-b]pyridine-2-carboxylate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of compound 145-C (23.41 g, 169.0 mmol) in acetonitrile (170 mL) was added methyl thioglycolate (16.2 mL, 178 mmol) and K2CO3 (46.72 g, 338 mmol). The mixture was heated under reflux for 3 h then filtered hot and the filter cake rinsed with acetonitrile. The filter cake was suspended in refluxing acetonitrile, filtered hot, and rinsed with additional acetonitrile. The combined filtrates were evaporated in vacuo, the residue triturated with warm water (250 mL), filtered, and rinsed with water. The solid was dissolved in warm methanol (500 mL), treated with charcoal, filtered, and evaporated in vacuo. The residue was triturated with ethanol (25 mL), filtered, washed with ethanol (25 mL), and dried in vacuo to afford compound 145-D as a brown powder (21.65 g, 62%). 1H-NMR (DMSO-d6): δ 3.83 (s, 3H), 6.91 (s, 2H), 7.52-7.59 (m, 1H), 8.40 (dd, 1H), 8.69 (dd, 1H); MS: m/z 209.1 (MH+).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 3 h
  3. filtrationthen filtered hot
  4. washthe filter cake rinsed with acetonitrile
  5. temperaturein refluxing acetonitrile
  6. filtrationfiltered hot
  7. washrinsed with additional acetonitrile
  8. customThe combined filtrates were evaporated in vacuo
  9. customthe residue triturated with warm water (250 mL)
  10. filtrationfiltered
  11. washrinsed with water
  12. dissolutionThe solid was dissolved in warm methanol (500 mL)
  13. additiontreated with charcoal
  14. filtrationfiltered
  15. customevaporated in vacuo
  16. customThe residue was triturated with ethanol (25 mL)
  17. filtrationfiltered
  18. washwashed with ethanol (25 mL)
  19. customdried in vacuo
  20. customto afford compound 145-D as a brown powder (21.65 g, 62%)

Sources & evidence

ORD record
ord-00ae7a28bede4b0ba25ab852d7827b35
Source dataset
uspto-grants-2016_09
Patent number
US09434711B2

Reaction notes

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