2-Bromopyridine → 1-(Pyridin-2-yl)piperazin-2-one

HRID 2114829ノート

反応式

HRID 2114829 の反応式
C(OC(N1C=CN(C)C(=O)C1)=O)C1C=CC=CC=1.BrC1C=CC=CN=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C(=O)([O-])[O-].[Cs+].[Cs+].C(OC([N:84]1[CH2:89][CH2:88][N:87]([C:90]2[CH:95]=[CH:94][CH:93]=[CH:92][N:91]=2)[C:86](=[O:96])[CH2:85]1)=O)C1C=CC=CC=1>O1CCOCC1.ClCCl.[OH-].[OH-].[Pd+2].C(O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N:91]1[CH:92]=[CH:93][CH:94]=[CH:95][C:90]=1[N:87]1[CH2:88][CH2:89][NH:84][CH2:85][C:86]1=[O:96]

参加物

11

反応物 5

HCID 79732-BromopyridineHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 58009754HCID 58009754、化合物HCID 69170789HCID 69170789、化合物

生成物 1

HCID 218650171-(Pyridin-2-yl)piperazin-2-one

試薬・触媒・溶媒 5

HCID 167845palladium(II) acetate触媒HCID 9942167Palladium hydroxide触媒HCID 702Ethanol溶媒HCID 6344Dichloromethane溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
110 °C

実験手順

A mixture of 4-benzyloxycarbonyl-1-methyl-pyrazin-2(1H)-one (3.0 g, 12.8 mmol), 2-bromopyridine (2.02 g, 12.8 mmol), palladium acetate (0.29 g, 1.28 mmol), xantphos (1.11 g, 1.92 mmol), cesium carbonate (6.26 g, 19.2 mmol) in anhydrous dioxane (13 mL) in a sealed vessel was heated in an oil bath at 110° C. for 6 hrs. The resultant reaction mixture was cooled to room temperature, diluted with dichloromethane, filtered, and concentrated under vacuum. The residual solid was subjected to column chromatography on silica gel eluting with a ethyl acetate-hexane gradient. Concentration of appropriate fractions provide the pyridine intermediate. A mixture of 4-benzyloxycarbonyl-1-pyridin-2-ylpiperazin-2-one (1.50 g, 4.94 mmol) and Pearlmans catalyst (0.7 g) in ethanol (50 mL) was stirred under an atmosphere of hydrogen (1 atm) at room temperature for one hour. The product mixture was filtered through a pad of Celite, and concentrated under vacuum to provide the titled compound.

後処理

  1. customThe resultant reaction mixture
  2. temperaturewas cooled to room temperature
  3. filtrationfiltered
  4. concentrationconcentrated under vacuum
  5. customConcentration of appropriate fractions provide the pyridine intermediate
  6. filtrationThe product mixture was filtered through a pad of Celite
  7. concentrationconcentrated under vacuum

出典と根拠

ORDレコード
ord-32d4c91a8d564ba5805550c200b3596c
出典データセット
uspto-grants-2008_10
特許番号
US07435735B2

反応ノート

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