Potassium thiocyanate → HCID 57813637, compound

HRID 447027Notes

Reaction equation

HRID 447027 reaction equation
[CH3:1][O:2][C:3](=[O:20])[C:4]1[CH:9]=[C:8]([C:10]2[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=2)[CH:7]=[C:6]([N+:16]([O-:18])=[O:17])[C:5]=1N.N([O-])=O.[Na+].[S-:25][C:26]#[N:27].[K+].C(=O)([O-])O.[Na+]>S(=O)(=O)(O)O.O.[Cu]SC#N>[CH3:1][O:2][C:3](=[O:20])[C:4]1[CH:9]=[C:8]([C:10]2[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=2)[CH:7]=[C:6]([N+:16]([O-:18])=[O:17])[C:5]=1[S:25][C:26]#[N:27]

Participants

8

Reactant 4

HCID 516872Potassium thiocyanateHCID 516892Sodium BicarbonateHCID 23668193Sodium NitriteHCID 59337640Methyl 2-amino-3-nitro-5-(3-pyridinyl)benzoate

Product 1

HCID 57813637HCID 57813637, compound

Reagents, catalysts & solvents 3

HCID 178514150Cuprous thiocyanateCatalystHCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent

Procedure

A suspension of 2-Amino-3-nitro-5-pyridin-3-yl-benzoic acid methyl ester (0.92 g, 3.37 mmol) in aqueous sulfuric acid (50% v/v, 9 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, 1.4 ml). The mixture was stirred in the cold for 1.5 h before being treated with a solution of potassium thiocyanate (0.42 g) in water (1.0 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 (0.71 g) in water (2.8 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-Nitro-5-pyridin-3-yl-2-thiocyanato-benzoic acid methyl ester was obtained as a pale yellow solid (0.78 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-dbec663b5d324f419305491e943e2fa9
Source dataset
uspto-grants-2013_07
Patent number
US08481544B2

Reaction notes

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