5-Bromonicotinamide → 5-Azidonicotinamide

HRID 1515568Notes

Reaction equation

HRID 1515568 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:10]=1)[C:7]([NH2:9])=[O:8].[N-:11]=[N+:12]=[N-:13].[Na+].CN[C@H]1CCCC[C@@H]1NC.O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>CCO.O.[Cu]I>[N:11]([C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:10]=1)[C:7]([NH2:9])=[O:8])=[N+:12]=[N-:13]

Participants

8

Reactant 4

HCID 18085-BromonicotinamideHCID 33557Sodium AzideHCID 13822957(1S,2S)-(+)-N,N'-Dimethylcyclohexane-1,2-diamineHCID 23667548Sodium Ascorbate

Product 1

HCID 594794565-Azidonicotinamide

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A solution of 5-bromonicotinamide (100 mg, 0.5 mmol), sodium azide (65 mg, 1.0 mmol), CuI (19.5 mg, 0.05 mmol), (1S,2S)—N1,N2-dimethylcyclohexane-1,2-diamine (11 mg, 0.08 mmol) and sodium ascorbate (5.0 mg, 0.03 mmol) in EtOH (0.7 mL) and H2O (0.3 mL) was degassed for 5 min before heated at reflux for 1.0 h. After cooled to rt, the mixture was extracted with EtOAc. The organic layer was washed with brine and dried over Na2SO4. After removal of the solvent, the crude was purified by silica gel column chromatography eluting with gradient EtOAc in hexanes (0-100%) to give 97A. 1H NMR (400 MHz, Methanol-d4) δ ppm 7.96-8.05 (m, 1H) 8.44 (d, J=2.64 Hz, 1H) 8.79 (d, J=1.76 Hz, 1H).

Workup

  1. temperaturebefore heated
  2. temperatureat reflux for 1.0 h
  3. extractionthe mixture was extracted with EtOAc
  4. washThe organic layer was washed with brine
  5. dry with materialdried over Na2SO4
  6. customAfter removal of the solvent
  7. customthe crude was purified by silica gel column chromatography
  8. washeluting with gradient EtOAc in hexanes (0-100%)

Sources & evidence

ORD record
ord-0183f4d77e8c4b2d904c1ca259438c19
Source dataset
uspto-grants-2012_07
Patent number
US08222453B2

Reaction notes

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