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

HRID 1707433노트

반응식

HRID 1707433 반응식
[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]

참가 물질

9

반응물 3

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

생성물 3

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

시약·촉매·용매 3

HCID 313Hydrochloric Acid용매HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

실험 절차

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%].

후처리

  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)

출처 및 근거

ORD 기록
ord-1564cc5c075442158bd058c9e8d6773a
출처 데이터셋
uspto-grants-1994_10
특허 번호
US05352792

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