1-Iodo-3-nitrobenzene → 4-Methyl-1-(3-nitrophenyl)piperazin-2-one

HRID 472505Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 472505
I[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1.[CH3:11][N:12]1[CH2:17][CH2:16][NH:15][C:14](=[O:18])[CH2:13]1.CN[C@@H]1CCCC[C@H]1NC.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>[Cu]I.O1CCOCC1>[CH3:11][N:12]1[CH2:17][CH2:16][N:15]([C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=2)[C:14](=[O:18])[CH2:13]1

Komponenten

7

Edukt 4

HCID 125741-Iodo-3-nitrobenzeneHCID 62657Potassium Phosphate, TribasicHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 137042831-Methyl-3-oxopiperazine

Produkt 1

HCID 674787904-Methyl-1-(3-nitrophenyl)piperazin-2-one

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

204 a) An oven dried tube was charged with 1-iodo-3-nitro-benzene (2.60 g, 10.4 mmol), 4-methyl-piperazin-2-one (1.00 g, 8.76 mmol), copper(I) iodide (85.0 mg, 0.446 mmol), (1R,2R)-N,N′-dimethyl-cyclohexane-1,2-diamine (0.14 mL, 0.89 mmol), potassium phosphate (3.75 g, 17.7 mmol) and 1,4-dioxane (10 mL). The tube was carefully evacuated and backflushed with nitrogen three times then sealed. The mixture was heated at 90° C. for 24 hours then cooled to room temperature and diluted with dichloromethane (20 mL). The mixture was filtered through a plug of diatomaceous earth and the filtrate was evaporated. The residue was purified via chromatography using an ISCO automated purification apparatus (silica gel column 40 g and 0%→4% methanol:dichloromethane). 4-Methyl-1-(3-nitro-phenyl)-piperazin-2-one was isolated as a red-brown waxy solid (1.13 g, 55%). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.20 (s, 1H), 8.13 (d, J=7.5 Hz, 1H), 7.73 (d, J=8.0 Hz, 1H), 7.57 (t, J=8.2 Hz, 1H), 3.79 (t, J=5.1 Hz, 2H), 3.31 (s, 2H), 2.83 (t, J=5.2 Hz, 2H), 2.42 (s, 3H). MS=236 (MH)+.

Aufarbeitung

  1. custom204 a) An oven dried tube
  2. customThe tube was carefully evacuated
  3. customthen sealed
  4. temperaturethen cooled to room temperature
  5. additiondiluted with dichloromethane (20 mL)
  6. filtrationThe mixture was filtered through a plug of diatomaceous earth
  7. customthe filtrate was evaporated
  8. customThe residue was purified via chromatography
  9. custompurification apparatus (silica gel column 40 g and 0%→4% methanol:dichloromethane)

Quellen und Nachweise

ORD-Eintrag
ord-13eb361456ce47b0be108d557af04e1b
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08633173B2

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