Ethylene Glycol → Tert-butyl 4-(5-bromopyridin-3-yl)piperazine-1-carboxylate

HRID 1044562Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1044562
[Br:1][C:2]1[CH:3]=[N:4][CH:5]=[C:6](I)[CH:7]=1.[N:9]1([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:14][CH2:13][NH:12][CH2:11][CH2:10]1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C(O)CO>C(O)(C)C.[Cu]I>[C:18]([O:17][C:15]([N:9]1[CH2:14][CH2:13][N:12]([C:6]2[CH:5]=[N:4][CH:3]=[C:2]([Br:1])[CH:7]=2)[CH2:11][CH2:10]1)=[O:16])([CH3:21])([CH3:19])[CH3:20]

Komponenten

7

Edukt 4

HCID 174Ethylene GlycolHCID 62657Potassium Phosphate, TribasicHCID 143452tert-Butyl piperazine-1-carboxylateHCID 8204093-Bromo-5-iodopyridine

Produkt 1

HCID 11653049Tert-butyl 4-(5-bromopyridin-3-yl)piperazine-1-carboxylateAusbeute 37 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 3776IsopropanolLösungsmittel

Versuchsvorschrift

A solution of 3-bromo-5-iodopyridine (13.0 g, 45.8 mmol), tert-butyl piperazine-1-carboxylate (8.53 g, 45.8 mmol), copper(I) iodide (0.871 g, 4.57 mmol), K3PO4 (19.46 g, 91.68 mmol), 1,2-ethanediol (5.1 mL, 91 mmol) in isopropyl alcohol (80 mL) in a sealed tube was heated at 80° C. in an oil bath for 2 days. After cooling to room temperature, the reaction mixture was filtered through celite. The filtrate was concentrated in vacuo. The residue was taken up in EtOAc and the solution was washed with saturated NaHCO3, dried (MgSO4) and concentrated. Purification by flash chromatography on silica gel (20% EtOAc/hexanes to 30% EtOAc/hexanes) afforded 5.75 g (37%) of desired product. MS calculated for C14H20BrN3O2: (M+H) 343; found 342.0, 344.0.

Aufarbeitung

  1. filtrationthe reaction mixture was filtered through celite
  2. concentrationThe filtrate was concentrated in vacuo
  3. washthe solution was washed with saturated NaHCO3
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customPurification by flash chromatography on silica gel (20% EtOAc/hexanes to 30% EtOAc/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-583448f49ff04c2c8f05d7547c739272
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08563582B2

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