Cesium carbonate → Dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2-YL)phosphine oxide

HRID 39606

反応式

HRID 39606 の反応式
ClC1C=CC(C2C=CC=CC=2)=CC=1.C(=O)([O-])[O-:15].[Cs+].[Cs+].[CH:20]1([P:26]([CH:43]2[CH2:48][CH2:47][CH2:46][CH2:45][CH2:44]2)[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=2[C:33]2[C:38]([O:39][CH3:40])=[CH:37][CH:36]=[CH:35][C:34]=2[O:41][CH3:42])[CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]1.O.NN>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O.CO.O1CCOCC1>[CH:43]1([P:26]([CH:20]2[CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]2)([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=2[C:33]2[C:38]([O:39][CH3:40])=[CH:37][CH:36]=[CH:35][C:34]=2[O:41][CH3:42])=[O:15])[CH2:44][CH2:45][CH2:46][CH2:47][CH2:48]1

参加物

10

反応物 4

HCID 10796Cesium carbonateHCID 163234-ChlorobiphenylHCID 24654Hydrazine hydrate (1:1)HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

生成物 1

HCID 67122844Dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2-YL)phosphine oxide収率 55.7%

試薬・触媒・溶媒 5

HCID 167845palladium(II) acetate触媒HCID 887Methanol溶媒HCID 962Water溶媒2 回HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

To the mixture of 4-chlorobiphenyl (15 mg, 0.079 mmol) and 1,4-dioxane (1 ml), water (0.1 ml), cesium carbonate (0.16 g, 0.48 mmol), sodium 1,3-dioxo-1,3-dihydro-isoindole-2-ylmethyl trifluoroborate (40 mg, 0.16 mmol), palladium(II) acetate (1.8 mg, 0.0079 mmol), and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (6.5 mg, 0.016 mmol) were added at room temperature, and then the obtained reaction mixture was stirred at 100° C. (an outer temperature) overnight. The reaction mixture was cooled to room temperature, and then hydrazine hydrate (40 mg, 0.79 mmol) and methanol (2 ml) were added thereto, followed by heating to reflux for 30 min. The reaction mixture was cooled to room temperature, and then water and ethyl acetate were added thereto, followed by filtration with celite. The organic layer of the filtrate was separated and washed with saline. The solvents were evaporated under reduced pressure from the organic layer, and then the obtained residue was purified with NH-silica gel column chromatography (ethyl acetate), thereby obtaining the entitled compound (7.7 mg, 53%) as the mixture with 2′-(dicyclohexyl-phosphinoyl)-2,6-dimethoxy-biphenyl (3.8 mg).

後処理

  1. additionwere added at room temperature
  2. customthe obtained reaction mixture
  3. temperatureThe reaction mixture was cooled to room temperature
  4. temperatureby heating
  5. temperatureto reflux for 30 min
  6. temperatureThe reaction mixture was cooled to room temperature
  7. filtrationfollowed by filtration with celite
  8. customThe organic layer of the filtrate was separated
  9. washwashed with saline
  10. customThe solvents were evaporated under reduced pressure from the organic layer
  11. customthe obtained residue was purified with NH-silica gel column chromatography (ethyl acetate)

出典と根拠

ORDレコード
ord-956f3d3c19b2483b86fcc550b00080c2
出典データセット
uspto-grants-2013_09
特許番号
US08524946B2

関連ノート

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