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

HRID 1707433ノート

反応式

HRID 1707433 の反応式
[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]

参加物

9

反応物 3

HCID 9526Methyl triflateHCID 2733832Lithium HexamethyldisilazideHCID 178477162HCID 178477162、化合物

生成物 3

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

試薬・触媒・溶媒 3

HCID 313Hydrochloric Acid溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

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%].

後処理

  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)

出典と根拠

ORDレコード
ord-1564cc5c075442158bd058c9e8d6773a
出典データセット
uspto-grants-1994_10
特許番号
US05352792

反応ノート

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