Sulfuric acid magnesium salt (1:1) → 3-Bromo-5-chlorothieno[3,2-b]pyridine

HRID 226084Notes

Reaction equation

HRID 226084 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]2[CH:8]=[CH:9][S:10][C:5]2=[CH:4][CH:3]=1.C(=O)(O)[O-].[Na+].P([O-])([O-])(O)=O.[K+].[K+].S([O-])([O-])(=O)=O.[Mg+2].[Br:29]Br>C(Cl)Cl.O.C(Cl)(Cl)Cl>[Br:29][C:8]1[C:6]2=[N:7][C:2]([Cl:1])=[CH:3][CH:4]=[C:5]2[S:10][CH:9]=1

Participants

9

Reactant 5

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 24408Bromine2×HCID 24450Potassium Phosphate, DibasicHCID 516892Sodium BicarbonateHCID 124155685-Chlorothieno[3,2-b]pyridine

Product 1

HCID 714643393-Bromo-5-chlorothieno[3,2-b]pyridineYield 54.2%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Procedure

1.00 g of 5-Chloro-thieno[3,2-b]pyridine (5.91 mmol), 497 mg of sodium bicarbonate (5.91 mmol), 1.54 g of potassium hydrogenphosphate (8.87 mmol) and 1.07 g of magnesium sulfate (8.87 mmol) are placed in a flask with 50 ml of chloroform. The reaction mixture is stirred under reflux for 30 min. 0.55 ml of Bromine (10.82 mmol) is added and stirred under reflux overnight. 0.55 ml of Additional bromine (10.82 mmol) is added and stirred under reflux for 1 day. The reaction mixture is cooled to room temperature and water and CH2Cl2 are added. Organic layer is separated. The water layer is adjusted to pH=14 with 5N NaOH and extracted with CH2Cl2. All organic layers are combined together and dried over Na2SO4 and evaporated. The crude product is applied onto a silica-gel chromatography column (Hexane:AcOEt=5:1) to give 796 mg of the title compound (54%). 1H-NMR (CDCl3): 8.12 (d, 1H, J=7.9 Hz), 7.81 (s, 1H), 7.36 (d, 1H, J=7.9 Hz) ppm.

Workup

  1. temperatureunder reflux for 30 min
  2. stirringstirred
  3. temperatureunder reflux overnight
  4. stirringstirred
  5. temperatureunder reflux for 1 day
  6. customOrganic layer is separated
  7. extractionextracted with CH2Cl2
  8. dry with materialdried over Na2SO4
  9. customevaporated

Sources & evidence

ORD record
ord-a644666bc4fe44fcaa46dc18d521dacb
Source dataset
uspto-grants-2009_07
Patent number
US07557103B2

Reaction notes

Loading…