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

HRID 1044562노트

반응식

HRID 1044562 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 3776Isopropanol용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-583448f49ff04c2c8f05d7547c739272
출처 데이터셋
uspto-grants-2013_10
특허 번호
US08563582B2

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