1-Bromo-4-iodobenzene → 1-(4-Bromophenyl)-cis-3,5-dimethylpiperazine

HRID 447317

Reaktionsgleichung

Reaktionsgleichung von HRID 447317
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.C1C=CC2C(C3C(O)=CC=C4C=3C=CC=C4)=C(O)C=CC=2C=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[CH3:39][C@H:40]1[CH2:45][NH:44][CH2:43][C@@H:42]([CH3:46])[NH:41]1>CCOC(C)=O.[Cu]I.CN(C=O)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:44]2[CH2:43][C@H:42]([CH3:46])[NH:41][C@H:40]([CH3:39])[CH2:45]2)=[CH:4][CH:3]=1

Komponenten

8

Edukt 4

HCID 115221-Bromo-4-iodobenzeneHCID 11762BinolHCID 62657Potassium Phosphate, TribasicHCID 6950261rel-(2R,6S)-2,6-dimethylpiperazine

Produkt 1

HCID 667303611-(4-Bromophenyl)-cis-3,5-dimethylpiperazineAusbeute 60,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A microwave vial was charged with 1-bromo-4-iodobenzene (1.0 g, 3.5 mmol), CuI (0.135 g, 0.707 mmol), BINOL (0.202 g, 0.707 mmol), and K3PO4 (1.5 g. 7.1 mmol). The vial was capped and then evacuated and backfilled with Ar. Cis-2,6-dimethylpiperazine (0.605 g, 5.30 mmol) and DMF (4 mL) were then added. The resulting mixture was stirred at rt for 4 d. The mixture was diluted with EtOAc, filtered through a cake of Celite and the filtrate was concentrated to give the crude product. Crude product was purified by flash chromatography using MeOH/CH2Cl2 (2:98 to 15:85) to give the title compound as a red solid (567 mg, 59%). 1H NMR (400 MHz, MeOD) δ 7.33 (d, J=8.8 Hz, 2H), 6.89 (d, J=8.8 Hz, 2H), 3.63-3.60 (m, 2H), 3.18-3.07 (m, 2H), 2.40 (t, J=11.6 Hz, 2H), 1.23 (d, J=6.4 Hz, 6H); MS ESI 269.0 [M+H]+, calcd for [C12H17BrN2+H]+ 269.06.

Aufarbeitung

  1. customThe vial was capped
  2. customevacuated
  3. filtrationfiltered through a cake of Celite
  4. concentrationthe filtrate was concentrated
  5. customto give the crude product
  6. customCrude product was purified by flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-c652735f6b6d4920a38ce1c2f3fd31a9
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08481533B2

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