Picolinic acid → Diethyl 2-(6-methoxypyridin-2-yl)malonate

HRID 535664ノート

反応式

HRID 535664 の反応式
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][CH3:9])[N:3]=1.N1C=CC=CC=1C(O)=O.C(=O)([O-])[O-].[Cs+].[Cs+].[C:25]([O:33][CH2:34][CH3:35])(=[O:32])[CH2:26][C:27]([O:29][CH2:30][CH3:31])=[O:28].[NH4+].[Cl-]>O1CCOCC1.[Cu]I.C(OCC)(=O)C>[CH3:9][O:8][C:4]1[N:3]=[C:2]([CH:26]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[C:25]([O:33][CH2:34][CH3:35])=[O:32])[CH:7]=[CH:6][CH:5]=1

参加物

9

反応物 5

HCID 1018Picolinic acidHCID 7761Diethyl MalonateHCID 10796Cesium carbonateHCID 25517Ammonium ChlorideHCID 2568102-Bromo-6-methoxypyridine

生成物 1

HCID 59636709Diethyl 2-(6-methoxypyridin-2-yl)malonate

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 slurry of 2-bromo-6-methoxypyridine (1.8 g, 9.57 mmol), copper(I) iodide (0.16 g, 0.86 mmol), 2-picolinic acid (0.21 g, 1.72 mmol), cesium carbonate (4.7 g, 14.4 mmol) and diethyl malonate (4.4 mL, 28.7 mmol) in dioxane (15 mL) was heated at 95° C. for 4 days. After cooling to room temperature, ethyl acetate and saturated aqueous NH4Cl were added. The organic phase was separated and the aqueous phase extracted with ethyl acetate. The combined organic phases were dried over Na2SO4 and concentrated. The product was purified twice by flash chromatography (SiO2; heptane/ethyl acetate, gradient 0-80% and second chromatography using heptane/ethyl acetate gradient 0-20%) giving the product. Yield: 1.1 g (43%).

後処理

  1. customThe organic phase was separated
  2. extractionthe aqueous phase extracted with ethyl acetate
  3. dry with materialThe combined organic phases were dried over Na2SO4
  4. concentrationconcentrated
  5. customThe product was purified twice by flash chromatography (SiO2; heptane/ethyl acetate, gradient 0-80% and second chromatography using heptane/ethyl acetate gradient 0-20%)
  6. customgiving the product

出典と根拠

ORDレコード
ord-5b48b19c3ad64b2e866dd840931f9f3c
出典データセット
uspto-grants-2014_10
特許番号
US08859534B2

反応ノート

読み込み中…