Potassium thiocyanate → 3-(3,5-Dinitro-4-thiocyanato-phenyl)-pyridine

HRID 447020Notes

Reaction equation

HRID 447020 reaction equation
[N+:1]([C:4]1[CH:10]=[C:9]([C:11]2[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=2)[CH:8]=[C:7]([N+:17]([O-:19])=[O:18])[C:5]=1N)([O-:3])=[O:2].N([O-])=O.[Na+].[S-:24][C:25]#[N:26].[K+].C(=O)([O-])O.[Na+]>S(=O)(=O)(O)O.O.[Cu]SC#N>[N+:1]([C:4]1[CH:10]=[C:9]([C:11]2[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=2)[CH:8]=[C:7]([N+:17]([O-:19])=[O:18])[C:5]=1[S:24][C:25]#[N:26])([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 516872Potassium thiocyanateHCID 516892Sodium BicarbonateHCID 23668193Sodium NitriteHCID 578137352,6-Dinitro-4-pyridin-3-yl-aniline

Product 1

HCID 578136843-(3,5-Dinitro-4-thiocyanato-phenyl)-pyridine

Reagents, catalysts & solvents 3

HCID 178514150Cuprous thiocyanateCatalystHCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent

Procedure

A suspension of 2,6-Dinitro-4-pyridin-3-yl-aniline (1.24 g, 4.76 mmol) in aqueous sulfuric acid (50% v/v, 12 ml) was stirred at ambient temperature for 1 h before being cooled in an ice bath and treated over 5 min with an aqueous sodium nitrite solution (20% w/v, 2.0 ml). The mixture was stirred in the cold for 1.5 h before being treated with a solution of potassium thiocyanate (0.6 g) in water (1.4 ml) in one portion. The resultant mixture was stirred in the cold for 15 min and then added to a suspension of copper (I) thiocyanate (1.0 g) in water (4 ml) whilst cooling in an ice-bath. The mixture was stirred in the cold for 2 h and then heated to 70° C. for 20 min. After cooling to ambient temperature, the mixture was poured into a saturated aqueous solution of sodium hydrogen carbonate (200 ml) and extracted with ethyl acetate (3×100 ml) which was washed with brine (200 ml) and dried (MgSO4). The solvent was removed in vacuo to give a residue which was purified by flash chromatography (silica) eluting with 80% to 100% ethyl acetate in 40-60 petroleum ether. The 3-(3,5-Dinitro-4-thiocyanato-phenyl)-pyridine was obtained as a yellow solid (1.07 g, 74%).

Workup

  1. temperaturebefore being cooled in an ice bath
  2. stirringThe mixture was stirred in the cold for 1.5 h
  3. temperaturewhilst cooling in an ice-bath
  4. stirringThe mixture was stirred in the cold for 2 h
  5. temperatureheated to 70° C. for 20 min
  6. temperatureAfter cooling to ambient temperature
  7. extractionextracted with ethyl acetate (3×100 ml) which
  8. washwas washed with brine (200 ml)
  9. dry with materialdried (MgSO4)
  10. customThe solvent was removed in vacuo
  11. customto give a residue which
  12. customwas purified by flash chromatography (silica)
  13. washeluting with 80% to 100% ethyl acetate in 40-60 petroleum ether

Sources & evidence

ORD record
ord-6e8fbd083ce748d4b93e0149d1363407
Source dataset
uspto-grants-2013_07
Patent number
US08481544B2

Reaction notes

Loading…