Bromine → Ethyl 4-amino-2-bromo-6-methylthieno[2,3-b]pyridine-5-carboxylate

HRID 573586Notes

Reaction equation

HRID 573586 reaction equation
[NH2:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[N:5]=[C:4]2[S:14][CH:15]=[CH:16][C:3]=12.[Br:17]Br>C(O)(=O)C>[NH2:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[N:5]=[C:4]2[S:14][C:15]([Br:17])=[CH:16][C:3]=12

Participants

4

Reactant 2

HCID 24408BromineHCID 68323805Ethyl 4-amino-6-methylthieno[2,3-b]pyridine-5-carboxylate

Product 1

HCID 68323734Ethyl 4-amino-2-bromo-6-methylthieno[2,3-b]pyridine-5-carboxylateYield 87%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a stirred solution of ethyl 4-amino-6-methylthieno[2,3-b]pyridine-5-carboxylate (Description 65) (1 g, 4.23 mmol) in acetic acid (3 mL) was added bromine (0.65 mL, 12.70 mmol) and the resulting mixture stirred at RT overnight (ca. 18 h). The reaction was quenched by pouring the reaction mixture into water and the aqueous solution was basified with NaOH (5M) and diluted with ethyl acetate (30 mL). The organic layer was separated and the aqueous layer was re-extracted with ethyl acetate (20 mL×3). The combined organics were washed with saturated sodium thiosulphate solution, dried and concentrated. Purification by chromatography on silica, eluting with a gradient of 0-30% ethyl acetate in DCM afforded the title compound (1.16 g). LCMS (A) m/z: 315/317 [M+1]+, Rt 0.95 min (acidic).

Workup

  1. customThe reaction was quenched
  2. additionby pouring the reaction mixture into water
  3. additiondiluted with ethyl acetate (30 mL)
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was re-extracted with ethyl acetate (20 mL×3)
  6. washThe combined organics were washed with saturated sodium thiosulphate solution
  7. customdried
  8. concentrationconcentrated
  9. customPurification by chromatography on silica
  10. washeluting with a gradient of 0-30% ethyl acetate in DCM

Sources & evidence

ORD record
ord-e6c1134a44e6478ca606237198ff9971
Source dataset
uspto-grants-2015_05
Patent number
US09029545B2

Reaction notes

Loading…