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Methyl vinyl sulfone → (2S)-2-(1-methylethyl)-4-[3-(methyloxy)-4-nitrophenyl]-1-[2-(methylsulfonyl)-ethyl]piperazine

HRID 419674
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HRID 419674 반응식
[CH3:1][CH:2]([C@@H:4]1[NH:9][CH2:8][CH2:7][N:6]([C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[C:12]([O:19][CH3:20])[CH:11]=2)[CH2:5]1)[CH3:3].[CH:21]([S:23]([CH3:26])(=[O:25])=[O:24])=[CH2:22]>O1CCOCC1>[CH3:3][CH:2]([C@H:4]1[CH2:5][N:6]([C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[C:12]([O:19][CH3:20])[CH:11]=2)[CH2:7][CH2:8][N:9]1[CH2:22][CH2:21][S:23]([CH3:26])(=[O:25])=[O:24])[CH3:1]
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참가 물질

4

반응물 2

HCID 19354Methyl vinyl sulfone2회HCID 59452824(3S)-3-(1-methylethyl)-1-[3-(methyloxy)-4-nitrophenyl]piperazine

생성물 1

HCID 66649776(2S)-2-(1-methylethyl)-4-[3-(methyloxy)-4-nitrophenyl]-1-[2-(methylsulfonyl)-ethyl]piperazine수율 78.3%

시약·촉매·용매 1

HCID 312751,4-Dioxane용매

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온도
60 °C

실험 절차

(3S)-3-(1-Methylethyl)-1-[3-(methyloxy)-4-nitrophenyl]piperazine (0.355 g, 1.27 mmol) was dissolved in 15 mL of dioxane with stirring. Methyl vinyl sulfone (0.34 mL, 3.88 mmol) was added via syringe. The reaction was heated to 60° C. for 2.5 days. Additional methyl vinyl sulfone (0.68 mL, 7.76 mmol) was added, and the heat was increased to 90° C. The reaction was maintained at that temperature for one week. The reaction was cooled to rt and concentrated onto silica gel. Purification by flash chromatography afforded the title compound of step G (0.383 g, 0.994 mmol, 78%). 1H NMR (400 MHz, DMSO-d6) δ 7.84 (d, J=9.5 Hz, 1H), 6.53 (dd, J=9.5, 2.4 Hz, 1H), 6.40 (d, J=2.4 Hz, 1H), 3.86 (s, 3H), 3.77 (d, J=12.5 Hz, 1H), 3.66 (br. s., J=12.5 Hz, 1H), 3.28-3.39 (m, 1H), 3.13-3.24 (m, 1H), 3.00-3.13 (m, 2H), 2.88-3.00 (m, 5H), 2.77-2.88 (m, 1H), 2.39-2.51 (m, 1H), 2.17-2.26 (m, 1H), 1.93-2.07 (m, 1H), 0.96 (d, J=6.8 Hz, 3H), 0.85 (d, J=6.8 Hz, 3H).

후처리

  1. temperaturethe heat was increased to 90° C
  2. temperatureThe reaction was maintained at that temperature for one week
  3. temperatureThe reaction was cooled to rt
  4. concentrationconcentrated onto silica gel
  5. customPurification by flash chromatography

출처 및 근거

ORD 기록
ord-2c674ff8657a4b6eac2cb904b31f2fa2
출처 데이터셋
uspto-grants-2012_01
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08093239B2

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