Pyridine → 5-Bromo-1-(phenylsulfonyl)-1h-pyrrolo[2,3-b]pyridine-3-carbonitrile

HRID 1432324Notes

Reaction equation

HRID 1432324 reaction equation
[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[C:17]([Br:19])[CH:18]=[C:13]3[C:12]([CH:20]=O)=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.NO.Cl.[N:25]1C=CC=CC=1.[O-]S([O-])(=O)=O.[Mg+2].[Se](=O)=O>C(Cl)(Cl)Cl.CCO>[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[C:17]([Br:19])[CH:18]=[C:13]3[C:12]([C:20]#[N:25])=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

8

Reactant 5

HCID 1049PyridineHCID 24007Selenium Dioxide2×HCID 24083Sulfuric acid magnesium salt (1:1)HCID 443297Hydroxyamine hydrochlorideHCID 592397531H-Pyrrolo[2,3-b]pyridine-3-carboxaldehyde, 5-bromo-1-(phenylsulfonyl)-

Product 1

HCID 689524475-Bromo-1-(phenylsulfonyl)-1h-pyrrolo[2,3-b]pyridine-3-carbonitrileYield 64%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6212ChloroformSolvent2×

Procedure

To a refluxing mixture of 7 (6.00 g, 16.4 mmol), CHCl3 (30 mL), EtOH (12 mL) and NH2OH.HCl (2.28 g, 32.9 mmol) was added dropwise a solution of pyridine (2.66 mL, 32.9 mmol) in CHCl3 (9 mL). When the addition was complete, a Soxhlet extractor containing MgSO4 was attached and the refluxing continued for 6 h. Selenium dioxide (2.73 g, 24.6 mmol) was then added portionwise over 1 h during reflux. Each time selenium dioxide was added an exothermic reaction occurred. When the addition was complete the reaction mixture was heated at reflux overnight. More SeO2 (1.00 g, 9.0 mmol) was added in one portion and the reflux continued for a further 1.5 h. The reaction mixture was cooled, sorbent (HM-N, Jones chromatography) added and the solvent evaporated. Purification by means of SGC using dichloromethane:hexane (1:1) (gradient elution) gave the product 8 (3.80 g, 64%) as a white solid; 1H NMR (400 MHz, CDCl3) δ 8.56 (d, J=2.2 Hz, 1H), 8.22 (m, 3H), 8.16 (d, J=2.1 Hz, 1H), 7.68 (tt, J=7.5, 1.2 Hz, 1H), 7.56 (t, 7.5 Hz, 2H).

Workup

  1. additionWhen the addition
  2. temperatureduring reflux
  3. customan exothermic reaction
  4. additionWhen the addition
  5. temperaturewas heated
  6. temperatureat reflux overnight
  7. waitthe reflux continued for a further 1.5 h
  8. temperatureThe reaction mixture was cooled
  9. additionsorbent (HM-N, Jones chromatography) added
  10. customthe solvent evaporated
  11. customPurification by means of SGC

Sources & evidence

ORD record
ord-e5014825dfb945c8adeaa2dcdc1bd6c1
Source dataset
uspto-grants-2009_11
Patent number
US07612086B2

Reaction notes

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