Sodium Azide → HCID 86663053, compound

HRID 2410815Notes

Reaction equation

HRID 2410815 reaction equation
[NH2:1][C:2]1[C:11]([C:12]2[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][CH:13]=2)=[N:10][C:9]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([C:27]([F:30])([F:29])[F:28])[CH:22]=2)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].N([O-])=O.[Na+].[N-:35]=[N+:36]=[N-].[Na+]>Cl.O>[N:1]([C:2]1[C:11]([C:12]2[CH:13]=[CH:14][C:15]([N+:18]([O-:20])=[O:19])=[CH:16][CH:17]=2)=[N:10][C:9]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([C:27]([F:30])([F:28])[F:29])[CH:22]=2)=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])=[N+:35]=[N-:36]

Participants

6

Reactant 3

HCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 66599487HCID 66599487, compound

Product 1

HCID 86663053HCID 86663053, compoundYield 89%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×

Procedure

A mixture of methyl 3-amino-2-(4-nitrophenyl)-6-(3-(trifluoromethyl)phenyl)isonicotinate (1 g, 2 4 mmol) in concentrated hydrochloric acid (20 mL, 37%) was cooled in an ice bath and a solution of sodium nitrite (0.99 g, 14.4 mmol) in water (0.5 ml) was added in small portions. The orange-red solution was stirred for 20 min and then a solution of sodium azide (0.94 g, 14.4 mmol) in water (0.5 mL) was added in portions. A precipitate formed and, after 30 min, the reaction was partitioned between DCM and water. The organic phase was washed with brine (2×50 mL), sat. aq. Na2CO3 solution, water, brine and then dried with sodium sulfate. Removal of the solvent followed by silica gel chromatography (elution with 40% EtOAc in hexane) afforded methyl 3-azido-2-(4-nitrophenyl)-6-(3-(trifluoromethyl)phenyl)-isonicotinate (1.0 g, 2 1 mmol, 89% yield). 1H NMR (500 MHz, chloroform-d) δ ppm 8.40 (2H, d, J=9.2), 8.33 (s, 1H), 8.29 (d, 1H, J=8.3), 8.22 (s, 1H), 8.07 (d, 2H, J=8.9), 7.74 (d, 1H, J=7.3), 7.66 (t, 1H, J=7.6), 4.12 (3H, s).

Workup

  1. temperaturewas cooled in an ice bath
  2. customA precipitate formed and, after 30 min
  3. customthe reaction was partitioned between DCM and water
  4. washThe organic phase was washed with brine (2×50 mL), sat. aq. Na2CO3 solution, water, brine
  5. dry with materialdried with sodium sulfate
  6. customRemoval of the solvent
  7. washfollowed by silica gel chromatography (elution with 40% EtOAc in hexane)

Sources & evidence

ORD record
ord-3f1b6f9663db4845aabc3ecad4e9efde
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

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