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

HRID 1624315

反応式

HRID 1624315 の反応式
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

参加物

10

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 5

HCID 167845palladium(II) acetate触媒HCID 16211205Tetraethylammonium chloride monohydrate触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-1d3f1359caaa46e2815d1420dfcc9050
出典データセット
uspto-grants-2014_07
特許番号
US08778967B2

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