N-bromobutanimide → 3-Bromo-7-chlorothieno[3,2-b]pyridine-6-carbonitrile

HRID 1178626Notes

Reaction equation

HRID 1178626 reaction equation
[Cl:1][C:2]1[C:7]([C:8]#[N:9])=[CH:6][N:5]=[C:4]2[CH:10]=[CH:11][S:12][C:3]=12.[Br:13]N1C(=O)CCC1=O.C(=O)(O)[O-].[Na+]>CN(C)C=O>[Br:13][C:10]1[C:4]2=[N:5][CH:6]=[C:7]([C:8]#[N:9])[C:2]([Cl:1])=[C:3]2[S:12][CH:11]=1

Participants

5

Reactant 3

HCID 67184N-bromobutanimide4×HCID 516892Sodium BicarbonateHCID 118164017-Chlorothieno[3,2-b]pyridine-6-carbonitrile

Product 1

HCID 114146423-Bromo-7-chlorothieno[3,2-b]pyridine-6-carbonitrileYield 25.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 7-chlorothieno[3,2-b]pyridine-6-carbonitrile (100 mg, 0.51 mmol) and N-bromosuccinimide (118 mg, 0.66 mmol) in 0.63 mL of dimethylformamide is stirred at room temperature for 4 days. Additional N-bromosuccinimide (118 mgs) is added and the reaction mixture is heated at 40° C. for 17 hours. Additional N-bromosuccinimide (118 mgs) is added and the reaction mixture is heated at 40° C. for 24 hours. Additional N-bromosuccinimide (118 mgs) is added and the reaction mixture is heated at 60° C. for 24 hours. The mixture is cooled to room temperature and treated with ice water and neutralized with aqueous saturated sodium bicarbonate. The resultant solid is purified by flash column chromatography eluting with 10% hexane in dichloromethane to provide 35 mg of 3-bromo-7-chlorothieno[3,2-b]pyridine-6-carbonitrile as a white solid, mp 176–178° C.; 1H NMR (DMSO-d6) δ 8.79 (s, 1H), 9.23 (s, 1H); MS 272.9, 274.8.

Workup

  1. temperaturethe reaction mixture is heated at 40° C. for 17 hours
  2. temperaturethe reaction mixture is heated at 40° C. for 24 hours
  3. temperaturethe reaction mixture is heated at 60° C. for 24 hours
  4. temperatureThe mixture is cooled to room temperature
  5. customThe resultant solid is purified by flash column chromatography
  6. washeluting with 10% hexane in dichloromethane

Sources & evidence

ORD record
ord-785b692e60b848718e6b541f6f0773b1
Source dataset
uspto-grants-2007_10
Patent number
US07276519B2

Reaction notes

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