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

HRID 1468927
ノート
印刷プレビュー

反応式

HRID 1468927 の反応式
[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]
参加物実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344
Dichloromethane
溶媒

実験手順

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 solution 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).

後処理

  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

出典と根拠

ORDレコード
ord-b8003c30309442989c73fe115035252c
出典データセット
uspto-grants-2015_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09006245B2

反応ノート

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