Triphenylphosphine → 6-bromo-4-methylene-3,4-dihydro-2H-pyrano[3,2-b]pyridine

HRID 2279270

反応式

HRID 2279270 の反応式
C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC([O-])=O.[K+].Br[C:26]1[C:31]([O:32][CH2:33][CH2:34][CH:35]=[CH2:36])=[CH:30][CH:29]=[C:28]([Br:37])[N:27]=1>CN(C=O)C.C(OCC)(=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[Br:37][C:28]1[N:27]=[C:26]2[C:35](=[CH2:36])[CH2:34][CH2:33][O:32][C:31]2=[CH:30][CH:29]=1

参加物

7

反応物 3

HCID 11776TriphenylphosphineHCID 517044Potassium AcetateHCID 584840892,6-Dibromo-3-(but-3-enyloxy)pyridine

生成物 1

HCID 584840716-bromo-4-methylene-3,4-dihydro-2H-pyrano[3,2-b]pyridine収率 22.4%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
105 °C

実験手順

To a stirred mixture of PPh3 (67.6 g, 0.258 mol), KOAc (42 g, 0.43 mol), Pd(OAc)2 (1.94 g, 8.6 mmol) and Et4NCI (28.6 g, 0.172 mmol), was added 2,6-dibromo-3-(but-3-enyloxy) pyridine (26.4 g, 0.086 mol) in anhydrous DMF (300 mL). The mixture was heated at 105° C. for 18 hours. After cooling to ambient temperature, the mixture was dissolved in Ethyl acetate, washed with water and brine, dried over Na2SO4, and concentrated in vacuo. The crude product was purified by silica gel chromatography (petroleum) to afford the title compound as oil (4.35 g, 22%). 1H NMR (400 Mz, DMSO-d6): δ 2.74 (t, J=5.4, 2H); 4.20 (t, J=6, 2H); 5.12 (s, 1H); 5.98 (s, 1H); 7.24 (d, J=7.5, 1H); 7.40 (d, J=7.5, 1H).

後処理

  1. temperatureAfter cooling to ambient temperature
  2. washwashed with water and brine
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. customThe crude product was purified by silica gel chromatography (petroleum)

出典と根拠

ORDレコード
ord-909bda4f2f054af3b22c56facb8f924b
出典データセット
uspto-grants-2015_09
特許番号
US09133218B2

関連ノート

読み込み中…