Sodium Hydroxide → 4-[5-(Methanesulfonyl)-4-methyl-4H-1,2,4-triazol-3-yl]pyridine

HRID 1453806Notes

Reaction equation

HRID 1453806 reaction equation
[CH3:1][N:2]1[C:6]([S:7][CH3:8])=[N:5][N:4]=[C:3]1[C:9]1[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=1.[Mn]([O-])(=O)(=O)=[O:16].[K+].[OH-:21].[Na+].O=[Si]=O>O.C(O)(=O)C.C(Cl)(Cl)Cl>[CH3:1][N:2]1[C:6]([S:7]([CH3:8])(=[O:16])=[O:21])=[N:5][N:4]=[C:3]1[C:9]1[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=1

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 24261SilicaHCID 516875Potassium PermanganateHCID 8659874-(4-Methyl-5-(methylthio)-4H-1,2,4-triazol-3-yl)pyridine

Product 1

HCID 221514774-[5-(Methanesulfonyl)-4-methyl-4H-1,2,4-triazol-3-yl]pyridine

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6212ChloroformSolvent

Conditions

Temperature
14.5 °C

Procedure

To a mechanically stirred solution of 4-[4-methyl-5-(methylthio)-4H-1,2,4-triazol-3-yl]pyridine (228 g) from the previous step, in a mixture of water (1.15 L) and acetic acid (1.15 L), was added portion-wise while cooling potassium permanganate (234 g), at such a rate as to maintain the temperature between 12 to 17° C. (ca. 45 min). The reaction mixture was then stirred at r.t. for 4 h before cooling on an ice-bath during the addition of a sodium hydroxide solution (5 N) over 2.5 h to set the pH to ca. 10. Dicalite® (100 g) and chloroform (1.6 L) was then added to the reaction mixture before filtration. The organic phase was separated from the filtrate and the aq. phase from the same was extracted with chloroform (2×1 L). The filter-cake was extracted twice with chloroform (2×1.5 L). The combined organic phases were dried over magnesium sulfate, filtered, and concentrated in vacuo to provide 158 g of the title compound as a white powder. Another crop (78 g, white powder) was obtained by extraction of the filter cake with chloroform (2×2 L) and concentration of this solution in vacuo. 1H NMR (DMSO-d6): 3.6 (s, 3H), 3.9 (s, 3H), 7.8 (s, 2H), 8.8 (s, 2H).

Workup

  1. additionwas added portion-wise
  2. customThe organic phase was separated from the filtrate
  3. extractionthe aq. phase from the same was extracted with chloroform (2×1 L)
  4. extractionThe filter-cake was extracted twice with chloroform (2×1.5 L)
  5. dry with materialThe combined organic phases were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6335703f50b14fb49a40a2a858e2e31c
Source dataset
uspto-grants-2009_01
Patent number
US07476684B2

Reaction notes

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