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Sodium Thiosulfate → (R)-tert-butyl 2-isopropyl-4-(4-(methoxycarbonyl)-5-(methylsulfonyl)-2-nitrophenyl)-3-oxopiperazine-1-carboxylate

HRID 1482952
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HRID 1482952 반응식
[CH:1]([C@@H:4]1[C:9](=[O:10])[N:8]([C:11]2[CH:16]=[C:15](SC)[C:14]([C:19]([O:21][CH3:22])=[O:20])=[CH:13][C:12]=2[N+:23]([O-:25])=[O:24])[CH2:7][CH2:6][N:5]1[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])([CH3:3])[CH3:2].[CH:33]1C=C(Cl)C=C(C(OO)=O)C=1.[O-:44][S:45]([O-:48])(=S)=O.[Na+].[Na+]>C(Cl)Cl>[CH:1]([C@@H:4]1[C:9](=[O:10])[N:8]([C:11]2[CH:16]=[C:15]([S:45]([CH3:33])(=[O:48])=[O:44])[C:14]([C:19]([O:21][CH3:22])=[O:20])=[CH:13][C:12]=2[N+:23]([O-:25])=[O:24])[CH2:7][CH2:6][N:5]1[C:26]([O:28][C:29]([CH3:32])([CH3:30])[CH3:31])=[O:27])([CH3:3])[CH3:2]
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참가 물질

5

반응물 3

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 89814992(R)-tert-butyl 2-isopropyl-4-(4-(methoxycarbonyl)-5-(methylthio)-2-nitrophenyl)-3-oxopiperazine-1-carboxylate

생성물 1

HCID 89827918(R)-tert-butyl 2-isopropyl-4-(4-(methoxycarbonyl)-5-(methylsulfonyl)-2-nitrophenyl)-3-oxopiperazine-1-carboxylate수율 85.4%

시약·촉매·용매 1

HCID 6344
Dichloromethane
용매

실험 절차

To a 2 L round-bottom flask containing (R)-tert-butyl 2-isopropyl-4-(4-(methoxycarbonyl)-5-(methylthio)-2-nitrophenyl)-3-oxopiperazine-1-carboxylate (crude 91.7 g, 0.196 mol) in CH2Cl2 (1 L) was added m-CPBA (84.6 g, 0.49 mmol, 2.5 eq). The mixture was stirred at rt overnight. Sat. Na2S2O3 was added slowly to quench the reaction. The mixture was extracted with CH2Cl2 (4×3 L). The combined organic layers were washed successively with Na2S2O3 solution (500 mL), NaHCO3 solution (500 mL) and brine, dried over anhydrous Na2SO4, filtered and concentrated under vacuum. The residue was purified by column chromatography on silica gel eluting with dichloromethane to give (R)-tert-butyl 2-isopropyl-4-(4-(methoxycarbonyl)-5-(methylsulfonyl)-2-nitrophenyl)-3-oxopiperazine-1-carboxylate (83.7 g, 85.4% yield) as a yellow solid. LC-MS MS (ESI) m/z 444.0 [M−56+H]+, 522.1 [M+Na]+. 1H NMR (CDCl3 300 MHz): δ 8.29 (s, 1H), 8.12 (s, 1H), 4.61-4.17 (m, 2H), 4.00-3.94 (m, 4H), 3.70-3.60 (m, 1H), 3.51-3.43 (m, 4H), 2.39-2.32 (m, 1H), 1.50 (s, 9H), 1.07 (d, J=6.9 Hz, 3H), 1.01 (d, J=6.9 Hz, 3H).

후처리

  1. customto quench
  2. customthe reaction
  3. extractionThe mixture was extracted with CH2Cl2 (4×3 L)
  4. washThe combined organic layers were washed successively with Na2S2O3 solution (500 mL), NaHCO3 solution (500 mL) and brine
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe residue was purified by column chromatography on silica gel eluting with dichloromethane

출처 및 근거

ORD 기록
ord-16326211a4fb446eaefb96c4845cdc4d
출처 데이터셋
uspto-grants-2016_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09416135B2

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