Potassium Carbonate → 4-ethyl-8-methoxy-1H-pyrano[3,4-c]pyridine

HRID 357506ノート

反応式

HRID 357506 の反応式
[CH2:1]([O:5][CH2:6][C:7]1[C:8]([O:14][CH3:15])=[N:9][CH:10]=[CH:11][C:12]=1I)[CH:2]=[CH:3][CH3:4].C(=O)([O-])[O-].[K+].[K+]>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Rh]Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:3]([C:2]1[C:12]2[C:7](=[C:8]([O:14][CH3:15])[N:9]=[CH:10][CH:11]=2)[CH2:6][O:5][CH:1]=1)[CH3:4]

参加物

7

反応物 2

HCID 11430Potassium CarbonateHCID 544155093-(But-2-enyloxymethyl)-4-iodo-2-methoxypyridine

生成物 1

HCID 106315694-ethyl-8-methoxy-1H-pyrano[3,4-c]pyridine

試薬・触媒・溶媒 4

HCID 70681Tetrabutylammonium Chloride触媒HCID 167845palladium(II) acetate触媒HCID 178479813HCID 178479813、化合物触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
90 °C

実験手順

A mixture of 3-(but-2-enyloxymethyl)-4-iodo-2-methoxy-pyridine (228 g, 0.714 mol), potassium carbonate (200 g, 1.45 mol) and tetrabutylammonium chloride (100 g, 0.36 mol) in N,N-dimethylformamide (3.5 L) is purged with nitrogen for 20 min prior to the addition of palladium(II) acetate (3.75 g, 0.0167 mol) and tris(triphenylphosphine) rhodium(I) chloride (5.31 g, 0.00574 mol). The mixture is heated at 90° C. for about 4 h, cooled to below 50° C. and filtered through a pad of Celite®. The pad is washed with tert-butyl methyl ether (200 ml). The filtrate is washed with water (4×3 L), dried over sodium sulfate (260 g) and concentrated to a dark oil that is vacuum distilled (about 85°-98° C., about 6 mm Hg) to provide 4-ethyl-8-methoxy-1H-pyrano[3,4-c]pyridine as a yellow-orange oil which contains a 14.3:1 ratio of 4-ethyl-8-methoxy-1H-pyrano[3,4-c]pyridine to the corresponding double bond isomer, 4-ethylidene-8-methoxy-3,4-dihydro-1H-pyrano[3,4-c]pyridine.

後処理

  1. customis purged with nitrogen for 20 min
  2. temperaturecooled to below 50° C.
  3. filtrationfiltered through a pad of Celite®
  4. washThe pad is washed with tert-butyl methyl ether (200 ml)
  5. washThe filtrate is washed with water (4×3 L)
  6. dry with materialdried over sodium sulfate (260 g)
  7. concentrationconcentrated to a dark oil that
  8. distillationdistilled (about 85°-98° C., about 6 mm Hg)

出典と根拠

ORDレコード
ord-d7633b52d1c5453e905c31dfe8d11945
出典データセット
uspto-grants-1998_11
特許番号
US05840898

反応ノート

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