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

HRID 39606

Reaction equation

HRID 39606 reaction equation
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

Participants

10

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 887MethanolSolventHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-956f3d3c19b2483b86fcc550b00080c2
Source dataset
uspto-grants-2013_09
Patent number
US08524946B2

Linked notes

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