碳酸氢铯 → Dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2-YL)phosphine oxide

HRID 39607

反应方程式

HRID 39607 反应方程式
BrC1C=CC=CC=1[O:8]C.C(=O)([O-])[O-].[Cs+].[Cs+].[CH:16]1([P:22]([CH:39]2[CH2:44][CH2:43][CH2:42][CH2:41][CH2:40]2)[C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=2[C:29]2[C:34]([O:35][CH3:36])=[CH:33][CH:32]=[CH:31][C:30]=2[O:37][CH3:38])[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1.O.NN>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O.CO.O1CCOCC1>[CH:39]1([P:22]([CH:16]2[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]2)([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=2[C:29]2[C:34]([O:35][CH3:36])=[CH:33][CH:32]=[CH:31][C:30]=2[O:37][CH3:38])=[O:8])[CH2:40][CH2:41][CH2:42][CH2:43][CH2:44]1

参与物

10

反应物 4

HCID 10796碳酸氢铯HCID 113582-溴苯甲醚HCID 24654水合肼HCID 112698722-双环己基膦-2',6'-二甲氧基联苯

产物 1

HCID 67122844Dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2-YL)phosphine oxide收率 45.4%

试剂、催化剂与溶剂 5

HCID 167845palladium acetate催化剂HCID 887(5BETA,17BETA)-17-羟基-17-(甲基-D3)-2'H-雄甾-2-烯并[3,2-C]吡唑-5'(1'H)-酮溶剂HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂2 次HCID 8857乙酸乙酯溶剂HCID 312751,4-二氧六环溶剂

反应条件

温度
95 °C

实验过程

To the mixture of 2-bromoanisole (0.020 ml, 0.16 mmol) and 1,4-dioxane (2 ml), water (0.2 ml), cesium carbonate (0.32 g, 0.97 mmol), sodium 1,3-dioxo-1,3-dihydro-isoindole-2-ylmethyl trifluoroborate (81 mg, 0.32 mmol), palladium(II) acetate (3.6 mg, 0.016 mmol), and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (13 mg, 0.032 mmol) were added, and then the obtained reaction mixture was stirred at 95° C. (an outer temperature) overnight. The reaction mixture was cooled to room temperature, and then hydrazine hydrate (0.039 ml, 0.81 mmol) and methanol (2 ml) were added thereto, followed by heating to reflux for 1 hour. The reaction mixture was cooled to room temperature, and then water and ethyl acetate were added to the reaction mixture, 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 (heptane:ethyl acetate=1:4), thereby obtaining the entitled compound (4.1 mg, 19%) as the mixture with 2′-(dicyclohexyl-phosphinoyl)-2,6-dimethoxy-biphenyl (6.2 mg).

后处理

  1. additionwere added
  2. customthe obtained reaction mixture
  3. temperatureThe reaction mixture was cooled to room temperature
  4. temperatureby heating
  5. temperatureto reflux for 1 hour
  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 (heptane:ethyl acetate=1:4)

来源与证据

ORD记录
ord-d01713c474f74d42b87c525175407e98
来源数据集
uspto-grants-2013_09
专利号
US08524946B2

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