Picolinic acid → Diethyl (pyridin-2-yl)propanedioate

HRID 81070

반응식

HRID 81070 반응식
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.N1C=CC=CC=1C(O)=O.C(=O)([O-])[O-].[Cs+].[Cs+].[C:23]([O:31][CH2:32][CH3:33])(=[O:30])[CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26]>O1CCOCC1.C(OCC)(=O)C.[Cu]I>[N:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[CH:24]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[C:23]([O:31][CH2:32][CH3:33])=[O:30]

참가 물질

8

반응물 4

HCID 1018Picolinic acidHCID 7761Diethyl MalonateHCID 10796Cesium carbonateHCID 2211262-Iodopyridine

생성물 1

HCID 331545Diethyl (pyridin-2-yl)propanedioate수율 60.5%

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

실험 절차

A mixture of 2-iodopyridine (1.00 g, 4.88 mmol), picolinic acid (0.060 g, 0.488 mmol), copper(I) iodide (0.046 g, 0.244 mmol), cesium carbonate (4.77 g, 14.63 mmol) and diethyl malonate (1.563 g, 9.76 mmol) in dioxane (10 mL) was stirred under nitrogen at room temperature for 15 h. The mixture was diluted with ethyl acetate (200 mL), washed with saturated ammonium chloride (20 mL), water (20 mL), brine (20 mL), dried (MgSO4) and concentrated. Silica gel chromatography, loading with dichloromethane-hexanes (1:1) and eluting with 5 to 30% ethyl acetate in hexanes, gave diethyl 2-(pyridin-2-yl)malonate (700 mg, 42% yield). 1H NMR (400 MHz, CDCl3) δ ppm 8.58 (1H, δ, J=4.77 Hz), 7.71 (1H, dd, J=7.78, 1.51 Hz), 7.50 (1H, δ, J=7.78 Hz), 7.18-7.24 (1H, m), 4.94 (1H, s), 4.14-4.32 (4H, m, J=7.15, 7.15, 7.03, 3.51 Hz), 1.19-1.35 (6H, m); MS (ES+) m/z: 238 (M+H); LC retention time: 1.88 min (analytical HPLC Method A).

후처리

  1. washwashed with saturated ammonium chloride (20 mL), water (20 mL), brine (20 mL)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated
  4. washeluting with 5 to 30% ethyl acetate in hexanes

출처 및 근거

ORD 기록
ord-7a45419e5a7243959d4362c056890976
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08846673B2

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