Methanol → HCID 178437450, compound

HRID 1682564Notes

Reaction equation

HRID 1682564 reaction equation
[NH2:1][C:2]1[C:7]([N+:8]([O-])=O)=[C:6]([CH3:11])[CH:5]=[CH:4][N:3]=1.CO.O1C[CH2:17][CH2:16][CH2:15]1>[Ni]>[CH2:16]([C:17]1[NH:1][C:2]2=[N:3][CH:4]=[CH:5][C:6]([CH3:11])=[C:7]2[N:8]=1)[CH3:15]

Participants

5

Reactant 3

HCID 887MethanolHCID 8028TetrahydrofuranHCID 2431662-Amino-4-methyl-3-nitropyridine

Product 1

HCID 178437450HCID 178437450, compound

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Conditions

Temperature
100 °C

Procedure

10 g (65.3 mmol) of 2-amino-4-methyl-3-nitropyridine are hydrogenated in 40 ml of tetrahydrofuran and 40 ml of methanol in the presence of Raney nickel. The catalyst is filtered off, the solvent is removed, the residue is treated with ethanolic HCl solution and the precipitated 2,3-diamino-4-methylpyridine hydrochloride is filtered off with suction. 7 g of this hydrochloride are dissolved in 57 g of polyphosphoric acid (from 28.5 g of P2O5 and 28.5 g of H3PO4 (85% strength)) and treated with 1.26 ml of propionic acid, and the solution is stirred at 100° C. for 2 h. After cooling, it is poured into ice-water, rendered alkaline by addition of Na2CO3 and extracted several times with EA. The combined EA phases are washed with saturated NaCl solution, dried over Na2SO4 and concentrated and the residue is chromatographed on SiO2 (EA/MeOH 5:1). 4.2 g of the title compound result.

Workup

  1. filtrationThe catalyst is filtered off
  2. customthe solvent is removed
  3. additionthe residue is treated with ethanolic HCl solution
  4. filtrationthe precipitated 2,3-diamino-4-methylpyridine hydrochloride is filtered off with suction
  5. dissolution7 g of this hydrochloride are dissolved in 57 g of polyphosphoric acid (from 28.5 g of P2O5 and 28.5 g of H3PO4 (85% strength))
  6. additiontreated with 1.26 ml of propionic acid
  7. temperatureAfter cooling
  8. additionit is poured into ice-water
  9. additionby addition of Na2CO3
  10. extractionextracted several times with EA
  11. washThe combined EA phases are washed with saturated NaCl solution
  12. dry with materialdried over Na2SO4
  13. concentrationconcentrated
  14. customthe residue is chromatographed on SiO2 (EA/MeOH 5:1)

Sources & evidence

ORD record
ord-a825ff1e984141feb1a54ebcc06d8cc5
Source dataset
uspto-grants-1997_06
Patent number
US05635525

Reaction notes

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