Hydroxylamine → 2-Amino-4,6-dimethyl-3-nitropyridine

HRID 653636Notes

Reaction equation

HRID 653636 reaction equation
OS(O)(=O)=O.[CH3:6][C:7]1[CH:12]=[C:11]([CH3:13])[N:10]=[C:9]([NH:14][N+]([O-])=O)[CH:8]=1.[NH4+:18].[OH-:19].N[OH:21]>>[NH2:14][C:9]1[C:8]([N+:18]([O-:21])=[O:19])=[C:7]([CH3:6])[CH:12]=[C:11]([CH3:13])[N:10]=1

Participants

5

Reactant 4

HCID 787HydroxylamineHCID 1118Sulfuric AcidHCID 14923Ammonium HydroxideHCID 19385621N-(4,6-Dimethylpyridin-2-yl)nitramide

Product 1

HCID 2984722-Amino-4,6-dimethyl-3-nitropyridine

Conditions

Temperature
0 °C

Procedure

To 75 mL of stirred conc H2SO4 cooled to -5° C. (ice-salt bath) was added 4,6-dimethyl-2-nitroaminopyridine (13.2 g, 79 mmol) portion-wise at such a rate as to maintain the internal temperature below -3° C. The mixture was warmed to 0° C. until homogeneous (30 minutes) at which time tlc (SiO2, 1:1 EtOAc/hexanes on a NH4OH neutralized aliquot) indicated that the rearrangement was complete. The mixture was poured onto 400 g of crushed ice and the pH was adjusted to 5.5 by the addition of conc NH2OH. The resulting yellow slurry was cooled to 0° C., filtered, washed with cold water (50 mL), and dried at room temperature to give a mixture of the title compound and the 5-nitro isomer in a 55:45 ratio (determined by 1H NMR). This mixture was used directly in the next step.

Workup

  1. temperatureto maintain the internal temperature below -3° C
  2. filtrationfiltered
  3. washwashed with cold water (50 mL)
  4. customdried at room temperature
  5. customto give

Sources & evidence

ORD record
ord-47e1ce24442d4674b636f18530100e2a
Source dataset
uspto-grants-1992_07
Patent number
US05128327

Reaction notes

Loading…