Cesium carbonate → 1-[2,5-Bis(methyloxy)-4-nitrophenyl]-4-(1-methylethyl)piperazine

HRID 1014212Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1014212
Cl[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([N+:10]([O-:12])=[O:11])=[CH:4][C:3]=1[O:13][CH3:14].[CH:15]([N:18]1[CH2:23][CH2:22][NH:21][CH2:20][CH2:19]1)([CH3:17])[CH3:16].C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:14][O:13][C:3]1[CH:4]=[C:5]([N+:10]([O-:12])=[O:11])[C:6]([O:8][CH3:9])=[CH:7][C:2]=1[N:21]1[CH2:22][CH2:23][N:18]([CH:15]([CH3:17])[CH3:16])[CH2:19][CH2:20]1

Komponenten

6

Edukt 4

HCID 10796Cesium carbonateHCID 780131-IsopropylpiperazineHCID 813621-Chloro-2,5-dimethoxy-4-nitrobenzeneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

Produkt 1

HCID 594421271-[2,5-Bis(methyloxy)-4-nitrophenyl]-4-(1-methylethyl)piperazineAusbeute 76 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysator

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

1-chloro-2,5-bis(methyloxy)-4-nitrobenzene (3.25 g, 15 mmol, TCl America), isopropylpiperizine (3.84 g, 30 mmol, Oakwood Products), cesium carbonate (9.8 g, 30 mmol), Pd2dba3 (1.37 g, 1.5 mmol), and XANTPHOS (1.3 g, 2.25 mmol) were added to degassed dioxane (80 mL) and heated to 100° C. under a water cooled reflux condenser for 12 hours. The dioxane was removed under reduced pressure and the solids were partitioned between methylene chloride (500 mL) and water (500 mL). The organic layer was dried over sodium sulfate, taken to a residue under reduced pressure, and purified by chromatography on SiO2to give 1-[2,5-bis(methyloxy)-4-nitrophenyl]-4-(1-methylethyl)piperazine as a yellow solid (3.5 g, 11.3 mmol, 76% yield). 1H NMR (400 MHz, CDCl3) δ ppm 1.09 (d, J=6.60 Hz, 6 H), 2.69-2.73 (m, 4 H), 2.75 (d, J=6.60 Hz, 1 H), 3.23-3.32 (m, 4 H), 3.88 (s, 3 H), 3.94 (s, 3 H), 6.48 (s, 1 H), 7.55 (s, 1 H).

Aufarbeitung

  1. customto degassed dioxane (80 mL)
  2. temperaturecooled
  3. temperaturereflux condenser for 12 hours
  4. customThe dioxane was removed under reduced pressure
  5. customthe solids were partitioned between methylene chloride (500 mL) and water (500 mL)
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. custompurified by chromatography on SiO2to

Quellen und Nachweise

ORD-Eintrag
ord-9bb07c05cb8548be8278c6d19ba8869d
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07981903B2

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