N-bromobutanimide → Ethyl 4-amino-2-bromo-6-methyl-3-(3-methylphenyl)thieno[2,3-b]pyridine-5-carboxylate

HRID 573577Notes

Reaction equation

HRID 573577 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]=[C:16]([C:17]3[CH:22]=[CH:21][CH:20]=[C:19]([CH3:23])[CH:18]=3)[C:3]=12.[Br:24]N1C(=O)CCC1=O>C(Cl)Cl>[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:24])=[C:16]([C:17]3[CH:22]=[CH:21][CH:20]=[C:19]([CH3:23])[CH:18]=3)[C:3]=12

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 68323806Ethyl 4-amino-6-methyl-3-(3-methylphenyl)thieno[2,3-b]pyridine-5-carboxylate

Product 1

HCID 68324026Ethyl 4-amino-2-bromo-6-methyl-3-(3-methylphenyl)thieno[2,3-b]pyridine-5-carboxylateYield 82.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of ethyl 4-amino-6-methyl-3-(3-methylphenyl)thieno[2,3-b]pyridine-5-carboxylate (Description 57) (880 mg, 2.70 mmol) in DCM (10 mL) at RT was added dropwise N-bromosuccinimide (528 mg, 2.97 mmol) pre-dissolved in DCM (15 mL). The reaction mixture stirred at RT under nitrogen atmosphere for ca. 1 h. The reaction mixture was then quenched with saturated NaHCO3 aqueous solution and the aqueous layer separated and re-extracted with DCM (ca. 30 mL). The combined organic layer was then passed through a phase separator and the solvent removed in vacuo. Purification by chromatography on silica, eluting with a gradient of 0-40% ethyl acetate in cyclohexane afforded the title compound (900 mg). LCMS (A) m/z: 405/407 [M+1]+, Rt 1.55 min (acidic).

Workup

  1. customThe reaction mixture was then quenched with saturated NaHCO3 aqueous solution
  2. customthe aqueous layer separated
  3. extractionre-extracted with DCM (ca. 30 mL)
  4. customthe solvent removed in vacuo
  5. customPurification by chromatography on silica
  6. washeluting with a gradient of 0-40% ethyl acetate in cyclohexane

Sources & evidence

ORD record
ord-c8860a2feab54f88bcbf3a5bd5212aba
Source dataset
uspto-grants-2015_05
Patent number
US09029545B2

Reaction notes

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