Methyl iodide → Methyl 1-methyl-1,2,3-benzotriazole-5-carboxylate

HRID 433012Notes

Reaction equation

HRID 433012 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH2:6][C:7]2[C:8](=[CH:12][CH:13]=1)[N:9]=[N:10][N:11]=2)=[O:4].[H-].[Na+].[CH3:16]I>CN(C)C=O>[CH3:1][O:2][C:3]([C:5]1[CH:13]=[CH:12][C:8]2[N:9]([CH3:16])[N:10]=[N:11][C:7]=2[CH:6]=1)=[O:4]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 53445280Benzotriazole-6-carboxylic acid methyl ester

Product 1

HCID 54389555Methyl 1-methyl-1,2,3-benzotriazole-5-carboxylate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred, cold (0° C.) solution of 1,2,3-benzotriazole-5-carboxylic acid methyl ester (2.51 g) in dimethylformamide was added 60% sodium hydride (370 mg) portion wise. After 20 minutes, methyl iodide (0.87 mL) was added. The reaction was quenched by the addition of water after 30 minutes. The mixture was extracted with ethyl acetate; the extracts were washed with water, and brine, and dried (sodium sulfate). Filtration and concentration of the filtrate gave a residue from which 716 mg of 1-methyl-1H-benzotriazole-5-carboxylic acid methyl ester crystallized (hot ethyl acetate). The mother liquor was purified by flash chromatography (eluting with 3:2 hexanes/ethyl acetate) to give 890 mg of 2-methyl-2H-benzotriazole-5-carboxylic acid methyl ester and 490 mg of 3-methyl-3H-benzotriazole-5-carboxylic acid methyl ester. Structural assignments were made on the basis of proton NMR and nOe experiments.

Workup

  1. customThe reaction was quenched by the addition of water after 30 minutes
  2. extractionThe mixture was extracted with ethyl acetate
  3. washthe extracts were washed with water, and brine
  4. dry with materialdried (sodium sulfate)
  5. filtrationFiltration and concentration of the filtrate

Sources & evidence

ORD record
ord-9b390928b43d4d739792931283feb999
Source dataset
uspto-grants-2003_12
Patent number
US06664395B2

Reaction notes

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