Nitric Acid → HCID 22938709, compound

HRID 856649Notes

Reaction equation

HRID 856649 reaction equation
[N+]([O-])(O)=O.N([O-])=O.[Na+].[CH2:9]([N:13]1[C:17](S)=[N:16][N:15]=[C:14]1[CH2:19][OH:20])[CH2:10][CH2:11][CH3:12].C(=O)([O-])[O-].[Na+].[Na+]>O>[CH2:9]([N:13]1[CH:17]=[N:16][N:15]=[C:14]1[CH2:19][OH:20])[CH2:10][CH2:11][CH3:12]

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 10340Sodium CarbonateHCID 23668193Sodium NitriteHCID 178448731HCID 178448731, compound

Product 1

HCID 22938709HCID 22938709, compoundYield 81.8%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a mixture of 90% nitric acid (17 ml) and water (25 ml) was added sodium nitrite (0.07 g) and then 4-n-butyl-3-hydroxymethyl-5-mercapto-4H-1,2,4-triazole (10.0 g) was slowly added for 0.5 hours at 45° C. After cooling to room temperature, sodium carbonate was slowly added thereto to adjust pH to 7 at 0° C. The reaction mixure was concentrated under reduced pressure, methanol was added to the residue, and the precipitates were removed by filtration. The mixture was concentrated under reduced pressure, and the obtained residue was separated and purified by column chromatography (basic silica gel, ethanol:ethyl acetate 1:9), to give 4-n-butyl-3-hydroxymethyl-4H-1,2,4-triazole (6.78 g) as orange oil. To 4-n-butyl-3-hydroxymethyl-4H-1,2,4-triazole (6.78 g) was slowly added thionyl chloride (44 ml) at 0° C. The mixture was heated to reflux for 1 hour, and concentrated under reduced pressure. To the residue was added ethyl acetate, and the precipitated crystals were collected by filtration. The crystals were washed with ethyl acetate, to give 4-n-butyl-3-chloromethyl-4H-1,2,4-triazole hydrochloride (7.03 g) as pale yellow crystals.

Workup

  1. customto adjust pH to 7 at 0° C
  2. concentrationThe reaction mixure was concentrated under reduced pressure, methanol
  3. additionwas added to the residue
  4. customthe precipitates were removed by filtration
  5. concentrationThe mixture was concentrated under reduced pressure
  6. customthe obtained residue was separated
  7. custompurified by column chromatography (basic silica gel, ethanol:ethyl acetate 1:9)

Sources & evidence

ORD record
ord-80c50601342c4a098a74f197f5efe91c
Source dataset
uspto-grants-2007_08
Patent number
US07262185B2

Reaction notes

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