3-Chloroaniline → HCID 45487767, compound

HRID 733686Notes

Reaction equation

HRID 733686 reaction equation
Br[C:2]1[C:7]2[CH:8]=[CH:9][N:10]([CH3:11])[C:6]=2[C:5]([Br:12])=[CH:4][N:3]=1.[Cl:13][C:14]1[CH:15]=[C:16]([CH:18]=[CH:19][CH:20]=1)[NH2:17].C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C(OCC)(=O)C.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>[Br:12][C:5]1[C:6]2[N:10]([CH3:11])[CH:9]=[CH:8][C:7]=2[C:2]([NH:17][C:16]2[CH:18]=[CH:19][CH:20]=[C:14]([Cl:13])[CH:15]=2)=[N:3][CH:4]=1

Participants

7

Reactant 3

HCID 79323-ChloroanilineHCID 10796Cesium carbonateHCID 57840842HCID 57840842, compound

Product 1

HCID 45487767HCID 45487767, compoundYield 59.1%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)Catalyst2×HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 4,7-dibromo-1-methyl-1H-pyrrolo[3,2-c]pyridine (290 mg), 3-chloroaniline (153 mg), cesium carbonate (652 mg), tris(dibenzylidineacetone)dipalladium(0) (10 mg) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (6 mg) in dioxan (5 ml) was heated at reflux under nitrogen overnight. A further addition of tris(dibenzylidineacetone)dipalladium(0) (10 mg) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (6 mg) was made and the mixture refluxed for 4 hrs, then a repeat addition made and reflux continued for 2 hrs. The mixture was diluted with ethyl acetate (5 ml), filtered through Celite using ethylacetate and evaporate. The residue was dissolved in ethyl acetate and passed through silica gel eluting with ethyl acetate and evaporated. Purification of the residue by chromatography on Biotage, eluting with isohexane/dichloromethane 1:1, and evaporation gave the title compound (199 mg)

Workup

  1. temperaturewas heated
  2. temperatureat reflux under nitrogen overnight
  3. temperaturethe mixture refluxed for 4 hrs
  4. additiona repeat addition
  5. temperaturereflux
  6. filtrationfiltered through Celite
  7. customevaporate
  8. dissolutionThe residue was dissolved in ethyl acetate
  9. customevaporated
  10. customPurification of the residue by chromatography on Biotage
  11. washeluting with isohexane/dichloromethane 1:1, and evaporation

Sources & evidence

ORD record
ord-893013638f81483285e671224b444815
Source dataset
uspto-grants-2009_09
Patent number
US07589206B2

Reaction notes

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