Methyl triflate → 4-Acetylthiomethylthio-3-methyl-1,2,3-triazole

HRID 1707433Notes

Reaction equation

HRID 1707433 reaction equation
[C:1]([S:4][CH2:5][S:6][C:7]1[N:8]=[N:9][NH:10][CH:11]=1)(=[O:3])[CH3:2].[CH3:12][Si]([N-][Si](C)(C)C)(C)C.[Li+].F[C:23](F)(F)S(OC)(=O)=O>O1CCCC1.Cl.O>[C:1]([S:4][CH2:5][S:6][C:7]1[N:8]([CH3:12])[N:9]=[N:10][CH:11]=1)(=[O:3])[CH3:2].[C:1]([S:4][CH2:5][S:6][C:7]1[N:8]=[N:9][N:10]([CH3:23])[CH:11]=1)(=[O:3])[CH3:2].[C:1]([S:4][CH2:5][S:6][C:7]1[CH:11]=[N:10][N:9]([CH3:12])[N:8]=1)(=[O:3])[CH3:2]

Participants

9

Reactant 3

HCID 9526Methyl triflateHCID 2733832Lithium HexamethyldisilazideHCID 178477162HCID 178477162, compound

Product 3

HCID 100357914-Acetylthiomethylthio-2-methyl-1,2,3-triazoleYield 3%HCID 100816064-Acetylthiomethylthio-1-methyl-1,2,3-triazoleYield 14%HCID 104204334-Acetylthiomethylthio-3-methyl-1,2,3-triazoleYield 34%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 4-acetylthiomethylthio-1,2,3-triazole (6 g: 31.75 mMol.) in tetrahydrofuran (30 ml) is added dropwise at -78° C. a solution of 1M lithium bis(trimethylsilyl)amide in tetrahydrofuran (35 ml: 35 mMol.), and the mixture is stirred at the same temperature for 5 minutes and added methyl trifluoromethanesulfonate (4.0 ml: 35 mMol.). After stirring at the same temperature for 2 hours, the reaction mixture is diluted with 10% hydrochloric acid (26 ml) and water, and extracted with ethyl acetate. The extract is washed with aqueous sodium hydrogen carbonate and brine, dried over sodium sulfate, and concentrated. The residue is purified by silica gel chromatography (n-hexane: ethyl acetate=1:2) to give 4-acetylthiomethylthio-3-methyl-1,2,3-triazole [2.22 g; NMR δ(CDCl3) ppm: 2.32(s, 3H), 4.13(s, 5H), 7.77(s, 1H). IR ν(CHCl3) cm-1 : 1698, 1429, 1355, 1263, 1226, 1205, 1127, 1100, 957. mp. 37°-38° C. Yield: 34%], 4-acetylthiomethylthio-1-methyl-1,2,3-triazole [884 mg; NMR δ(CDCl3) ppm: 2.35(s, 3H), 4.11(s, 3H), 4.33(s, 2H), 7.59(s, 1H). IR ν(CHCl13) cm-1: 1691, 1434, 1354, 1285, 1131, 1106, 1048, 1031, 956. mp. 71°-72° C. Yield: 14%], and 4-acetylthiomethylthio-2-methyl-1,2,3-triazole [175 mg; NMR δ(CDCl13) ppm: 2.35 (s, 3H), 4.20(s, 3H), 4.30(s, 2H), 7.56(s, 1H). IR ν(CHCl3) cm-1 : 1691, 1446, 1369, 1130, 1006, 990, 956. Oil. Yield: 3%].

Workup

  1. stirringAfter stirring at the same temperature for 2 hours
  2. extractionextracted with ethyl acetate
  3. washThe extract is washed with aqueous sodium hydrogen carbonate and brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue is purified by silica gel chromatography (n-hexane: ethyl acetate=1:2)

Sources & evidence

ORD record
ord-1564cc5c075442158bd058c9e8d6773a
Source dataset
uspto-grants-1994_10
Patent number
US05352792

Reaction notes

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