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

HRID 2279270

반응식

HRID 2279270 반응식
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

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 6228Dimethylformamide용매HCID 8857Ethyl Acetate용매

반응 조건

온도
105 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-909bda4f2f054af3b22c56facb8f924b
출처 데이터셋
uspto-grants-2015_09
특허 번호
US09133218B2

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