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

HRID 39608

Reaction equation

HRID 39608 reaction equation
BrC1C=C(C2C=CC=CC=2)C=CC=1.[O:14]1CCOCC1.[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.O.C(OCC)(=O)C.CO>[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:14])[CH2:44][CH2:45][CH2:46][CH2:47][CH2:48]1

Participants

9

Reactant 4

HCID 164493-BromobiphenylHCID 24654Hydrazine hydrate (1:1)HCID 312751,4-DioxaneHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

Product 1

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

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 887MethanolSolventHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
94 °C

Procedure

To the mixture of 3-bromobiphenyl (0.020 ml, 0.12 mmol) and 1,4-dioxane (1.5 ml), water (0.15 ml), potassium phosphate tribasic n-hydrate (170 mg, 0.72 mmol), sodium 1,3-dioxo-1,3-dihydro-isoindole-2-ylmethyl trifluoroborate (60 mg, 0.24 mmol), palladium(II) acetate (2.7 mg, 0.012 mmol), and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (9.9 mg, 0.024 mmol) were added, and then the obtained reaction mixture was stirred at 94° C. (an outer temperature) overnight. The reaction mixture was cooled to room temperature, and then hydrazine hydrate (48 mg, 0.96 mmol) and methanol (2 ml) were added thereto, followed by heating to reflux for 40 min. The reaction mixture was cooled to room temperature, and then ethyl acetate and water 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 (ethyl acetate), thereby obtaining the entitled compound (11 mg, 51%) as the mixture with 2′-(dicyclohexyl-phosphinoyl)-2,6-dimethoxy-biphenyl (6.2 mg).

Workup

  1. additionwere added
  2. customthe obtained reaction mixture
  3. temperatureThe reaction mixture was cooled to room temperature
  4. temperatureby heating
  5. temperatureto reflux for 40 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-8bc20bd6395941389bf10f1441644e6e
Source dataset
uspto-grants-2013_09
Patent number
US08524946B2

Linked notes

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