Triphenylphosphine → HCID 86077235, compound

HRID 562875Notes

Reaction equation

HRID 562875 reaction equation
[C:1]1([P:7]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Br:20][C:21]1[CH:22]=[C:23]([P:27]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:24]=[CH:25][CH:26]=1.[Br-].[K+]>C(#N)C1C=CC=CC=1.[Ni](Br)Br>[Br-:20].[C:14]1([P:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[C:8]2[CH:13]=[C:12]([P+:27]([C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C:23]3[CH:22]=[CH:21][CH:26]=[CH:25][CH:24]=3)[CH:11]=[CH:10][CH:9]=2)[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 253877Potassium BromideHCID 11233124HCID 11233124, compound

Product 1

HCID 86077235HCID 86077235, compoundYield 78%

Reagents, catalysts & solvents 2

HCID 278492Nickel(II) bromideCatalystHCID 7505BenzonitrileSolvent2×

Procedure

To a solution of nickel (II) bromide (dry under vacuum for 2 h at 140° C.) (3.6 g, 16 mmol, 0.5 equiv) in benzonitrile (dry overnight on activated 4 A molecular sieves) (250 mL) was added triphenylphosphine (26.0 g, 49 mmol, 3 equiv). The solution was heated under reflux for 15 min and then cooled to room temperature. (3-bromophenyl)diphenylphosphine (2) (11.1 g, 32.5 mmol, 1.0 equiv) in benzonitrile (20 mL plus rinse 5 mL) was added to the solution. The resulting solution was heated under reflux for 4 h then cooled to room temperature. A 10% (w/w) aqueous solution of potassium bromide (250 mL) was added. The layers were separated, and the aqueous layer was washed two times with CH2Cl2 (250 mL). The organic layer was washed three times with water (100 mL) and dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. To the resulting solution was added hexane (750 mL) to precipitate the crude product. The precipitate was filtered and washed with hexane and then dissolved in CH2Cl2 (20 mL). Et2O (150 mL) was then added and the mixture was filtered. The resulting solid was purified by flash chromatography (MeOH/CH2Cl2, 0:100-10:90) to afford (3-diphenylphosphinophenyl)triphenylphosphonium bromide (3) (>95% purity) as a white solid (15.3 g, 78%), which was characterized as follows:

Workup

  1. temperatureThe solution was heated
  2. temperatureunder reflux for 15 min
  3. temperatureThe resulting solution was heated
  4. temperatureunder reflux for 4 h
  5. temperaturethen cooled to room temperature
  6. customThe layers were separated
  7. washthe aqueous layer was washed two times with CH2Cl2 (250 mL)
  8. washThe organic layer was washed three times with water (100 mL)
  9. dry with materialdried over anhydrous MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. additionTo the resulting solution was added hexane (750 mL)
  13. customto precipitate the crude product
  14. filtrationThe precipitate was filtered
  15. washwashed with hexane
  16. dissolutiondissolved in CH2Cl2 (20 mL)
  17. additionEt2O (150 mL) was then added
  18. filtrationthe mixture was filtered
  19. customThe resulting solid was purified by flash chromatography (MeOH/CH2Cl2, 0:100-10:90)

Sources & evidence

ORD record
ord-e99f939516f340c198a1fed2b77016b3
Source dataset
uspto-grants-2011_11
Patent number
US08067440B2

Reaction notes

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