Ethanol → Ethyl 3-aminothieno[2,3-b]pyridine-2-carboxylate

HRID 2112067Notes

Reaction equation

HRID 2112067 reaction equation
Cl[C:2]1[C:7]([C:8]#[N:9])=[CH:6][CH:5]=[CH:4][N:3]=1.[SH:10][CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13].C(=O)([O-])[O-].[Na+].[Na+].CCO>O>[NH2:9][C:8]1[C:7]2[C:2](=[N:3][CH:4]=[CH:5][CH:6]=2)[S:10][C:11]=1[C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

6

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 12185Ethyl ThioglycolateHCID 810792-Chloronicotinonitrile

Product 1

HCID 738459Ethyl 3-aminothieno[2,3-b]pyridine-2-carboxylateYield 96.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of 2-chloro-3-cyanopyridine (330 g, 2.3 mol), ethyl 2-mercaptoacetate (361.2 g, 3.0 mol), sodium carbonate (265 g, 2.5 mol) and EtOH (1.2L) was heated to reflux for 4.5 hours. The reaction mixture was cooled to ambient temperature and added to water (15L). The resultant precipitate was stirred for 30 minutes and then filtered. The filter cake was washed with two portions of water (2×2.5L) and dried to constant weight under vacuum at 45° C. to yield the title compound as a brown solid (493.1 g, 93.2%). δH (CDCl3) 8.68 (1H, dd, J 4.7, 1.2 Hz), 7.93 (1H, dd, J 8.5, 1.2 Hz), 7.29 (1H, dd, J 8.5, 4.7 Hz), 5.90 (2H, b), 4.38 (2H, q, J 7.0 Hz), 1.40 (3H, t, J 7.0 Hz). LCMS RT 2.9 minutes, 223 (M+H)+.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 4.5 hours
  3. filtrationfiltered
  4. washThe filter cake was washed with two portions of water (2×2.5L)
  5. customdried to constant weight under vacuum at 45° C.

Sources & evidence

ORD record
ord-de425d779afb41bca0ce78a338b75ca2
Source dataset
uspto-grants-2009_04
Patent number
US07521460B2

Reaction notes

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