Dimethylformamide → 4-Methylene-3,4-dihydro-2H-pyrano[3,2-b]pyridine

HRID 1624315

반응식

HRID 1624315 반응식
CN(C=O)C.Br[C:7]1[C:12]([O:13][CH2:14][CH2:15][CH:16]=[CH2:17])=[CH:11][CH:10]=[CH:9][N:8]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])(=O)C.[K+]>O.[Cl-].C([N+](CC)(CC)CC)C.CCOC(C)=O.[Cl-].[Na+].O.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:17]=[C:16]1[C:7]2=[N:8][CH:9]=[CH:10][CH:11]=[C:12]2[O:13][CH2:14][CH2:15]1

참가 물질

10

반응물 4

HCID 6228DimethylformamideHCID 11776TriphenylphosphineHCID 517044Potassium AcetateHCID 220185632-Bromo-3-(but-3-en-1-yloxy)pyridine

생성물 1

HCID 220186834-Methylene-3,4-dihydro-2H-pyrano[3,2-b]pyridine수율 67.5%

시약·촉매·용매 5

HCID 167845palladium(II) acetate촉매HCID 16211205Tetraethylammonium chloride monohydrate촉매HCID 962Water용매HCID 8857Ethyl Acetate용매HCID 57417360Sodium chloride; water용매

실험 절차

An anhydrous DMF solution (120 mL) of 2-bromo-3-but-3-enyloxy-pyridine (6.43 g, 28.2 mmol) in a round bottom schlenk flask was degassed with argon using the freeze/pump/thaw method. To this freshly degassed solution was added triphenylphosphine (2.66 g, 10.2 mmol), palladium acetate (696 mg, 3.10 mmol), potassium acetate (13.84 g, 141 mmol), and tetraethylammoniumchloride hydrate (9.35 g, 56.4 mmol). The resultant mixture was heated at 110° C. under argon for 18 hours. The reaction mixture was cooled to room temperature and diluted with EtOAc (300 mL), brine (120 mL) and H2O (60 mL). The organic phase was separated and washed with brine (3×120 mL) and dried over Na2SO4. Evaporation of the solvent and purification of the residue by flash chromatograph on silica gel (Hexanes/EtOAc, 95:5) afforded 4-methylene-3,4-dihydro-2H-pyrano[3,2-b]pyridine (2.8 g, 67%) as a white solid. 1H NMR (CDCl3) δ 2.79-2.86 (m, 2H), 4.25 (t, 2H, J=5.7 Hz), 5.08 (d, 1H, J=1.6 Hz), 6.19 (d, 1H, J=1.6 Hz), 7.08-7.17 (m, 2H), 8.20 (dd, 1H, J=4.7, 1.6 Hz).

후처리

  1. customThe organic phase was separated
  2. washwashed with brine (3×120 mL)
  3. dry with materialdried over Na2SO4
  4. customEvaporation of the solvent and purification of the residue by flash chromatograph on silica gel (Hexanes/EtOAc, 95:5)

출처 및 근거

ORD 기록
ord-1d3f1359caaa46e2815d1420dfcc9050
출처 데이터셋
uspto-grants-2014_07
특허 번호
US08778967B2

연결된 노트

불러오는 중…