Triphenylphosphine Oxide → Triphenylphosphine

HRID 436348Notes

Reaction equation

HRID 436348 reaction equation
[C:1]1([P:7](=O)([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.[Si](Cl)(Cl)(Cl)Cl.[H][H]>[S]>[C:14]1([P:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

5

Reactant 3

HCID 13097Triphenylphosphine OxideHCID 24816Silicon tetrachlorideHCID 178418361HCID 178418361, compound

Product 1

HCID 11776TriphenylphosphineYield 86.9%

Reagents, catalysts & solvents 1

HCID 5362487SulfurCatalyst

Conditions

Temperature
250 °C

Procedure

To an oven-dried 50-ml autoclave liner were added 16.68 g of triphenylphosphine oxide (.06 mole) and 0.057 g of sulfur (.0018 mole). The solids were treated with 11.12 g of silicon tetrachloride (.066 mole) and the mixture was placed in an autoclave which was then charged to a pressure of 715 p.s.i.g. (48 atm.) with hydrogen. The mixture was heated to 250°C for 15 hours at a maximum pressure of 77 atm. After cooling and venting, the reaction mixture was worked up by first partitioning between warm 30% by weight aqueous sodium hydroxide solution and toluene. The aqueous layer was extracted once with toluene and the combined organic layers were washed with water and with brine and dried over anhydrous sodium sulfate. Filtration and solvent removal gave 13.66 g (86.9%) of crude triphenylphosphine, mp 68°-77° which contained 2% triphenylphosphine oxide and 3% triphenylphosphine sulfide by gas-liquid chromatographic (glc) analysis. Recrystallization from methanol gave 11.25 g (71%) of purified triphenylphosphine, mp 75°-9°, still containing 1-2% triphenylphosphine sulfide by glc analysis.

Workup

  1. temperatureAfter cooling
  2. customby first partitioning
  3. temperaturebetween warm 30% by weight aqueous sodium hydroxide solution and toluene
  4. extractionThe aqueous layer was extracted once with toluene
  5. washthe combined organic layers were washed with water and with brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationFiltration and solvent removal

Sources & evidence

ORD record
ord-dd467331b3034d818264ef285eb2b622
Source dataset
uspto-grants-1977_02
Patent number
US04008282

Reaction notes

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