m-Chloroperbenzoic acid → HCID 86612973, compound

HRID 1409107Notes

Reaction equation

HRID 1409107 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[CH:10]=[CH:9][NH:8][C:5]2=[N:6][CH:7]=1.ClC1C=CC=C(C(OO)=[O:19])C=1>CCOC(C)=O>[Cl:1][C:2]1[CH:3]=[C:4]2[CH:10]=[CH:9][NH+:8]([O-:19])[C:5]2=[N:6][CH:7]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 242292135-Chloro-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 86612973HCID 86612973, compoundYield 24%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Procedure

To 5-chloro-1H-pyrrolo[2,3-b]pyridine (10.0 g, 65.6 mmol) in EtOAc (70 mL) at 0° C. was added dropwise over 15 h a solution of m-chloroperbenzoic acid (57%, 17.9 g, 104 mmol) in EtOAc (80 mL). The reaction mixture was stirred for 20 h at RT. Then, the mixture was cooled to −40° C. and the solids were filtered off and rinsed with cold EtOAc. The solid was taken up in water (70 mL) and treated dropwise with 30% aq. K2CO3 until pH was 11. The solution was warmed for 30 min, cooled to 0° C., filtered and dried in vacuo. Analysis (NMR) indicated the presence of m-chloroperbenzoic acid. The solid was taken up in 10% MeOH in DCM and washed with 30% aq. K2CO3 until all m-chlorobenzoic acid was removed. The organic layer was dried over Na2SO4, filtered and concentrated to provide 2.61 g (24% yield) of 5-chloro-1H-pyrrolo[2,3-b]pyridine-N-oxide (C). The combined mother liquors were concentrated. Flash chromatography (5% MeOH-DCM) provided and additional 1.49 g (13% yield) contaminated with ˜10% of the benzoic acid. LC/MS (M+H+) 168.76.

Workup

  1. temperatureThen, the mixture was cooled to −40° C.
  2. filtrationthe solids were filtered off
  3. washrinsed with cold EtOAc
  4. additiontreated dropwise with 30% aq. K2CO3 until pH was 11
  5. temperatureThe solution was warmed for 30 min
  6. temperaturecooled to 0° C.
  7. filtrationfiltered
  8. customdried in vacuo
  9. washwashed with 30% aq. K2CO3 until all m-chlorobenzoic acid
  10. customwas removed
  11. dry with materialThe organic layer was dried over Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-8e198235da0a4e7d8dfe1f150f726700
Source dataset
uspto-grants-2014_12
Patent number
US08921376B2

Reaction notes

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