Sodium Hydroxide → 4-Nitro-2-(1h-1,2,4-triazol-1-yl)pyridine

HRID 1640109Notes

Reaction equation

HRID 1640109 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][N+:7]([O-])=[C:6]([N:11]2[CH:15]=[N:14][CH:13]=[N:12]2)[CH:5]=1)([O-:3])=[O:2].P(Cl)(OCC)OCC.[OH-].[Na+]>C(Cl)(Cl)Cl>[N+:1]([C:4]1[CH:9]=[CH:8][N:7]=[C:6]([N:11]2[CH:15]=[N:14][CH:13]=[N:12]2)[CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 68530Ethyl phosphorochloridite2×HCID 667213864-nitro-2-(1H-1,2,4-triazol-1-yl)pyridine 1-oxide

Product 1

HCID 589024004-Nitro-2-(1h-1,2,4-triazol-1-yl)pyridineYield 32.4%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a solution of 4-nitro-2-(1H-1,2,4-triazol-1-yl)pyridine 1-oxide (0.643 g, 3.10 mmol) in CHCl3 (30 mL) at 0° C. was added diethyl chlorophosphite (1.35 mL, 9.31 mmol). The reaction mixture was allowed to stir at rt for 72 h. Additional diethyl chlorophosphite (1.35 mL, 9.31 nmmol) was added and the reaction mixture was heated at 80° C. for 18 h. The reaction mixture was cooled to 0° C., basified by the addition of 1N NaOH solution and extracted with DCM. The organic solutions were combined, washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography. The product was triturated with hexane to provide 4-nitro-2-(1H-1,2,4triazol-1-yl)pyridine (0.192 g, 32.3%). LCMS: (FA) ES+ 192.3.

Workup

  1. temperaturethe reaction mixture was heated at 80° C. for 18 h
  2. temperatureThe reaction mixture was cooled to 0° C.
  3. extractionextracted with DCM
  4. washwashed with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography
  9. customThe product was triturated with hexane

Sources & evidence

ORD record
ord-2ce9c616035b4e4d933f00887212e6a2
Source dataset
uspto-grants-2012_02
Patent number
US08110687B2

Reaction notes

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