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

HRID 81070

反応式

HRID 81070 の反応式
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]

参加物

8

反応物 4

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

生成物 1

HCID 331545Diethyl (pyridin-2-yl)propanedioate収率 60.5%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-7a45419e5a7243959d4362c056890976
出典データセット
uspto-grants-2014_09
特許番号
US08846673B2

関連ノート

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