Sodium Iodide → Bis(diphenylphosphine)methane monooxide

HRID 581452Notes

Reaction equation

HRID 581452 reaction equation
[CH:1]1[CH:2]=[CH:3][C:4]([P:7]([C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)[CH2:8][P:9]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)=[CH:5][CH:6]=1.BrCCBr.[OH-:32].[Na+].[Na+].[I-]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.ClCCl>[P:7]([CH2:8][P:9]([C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:32])([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:4]1[CH:3]=[CH:2][CH:1]=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 5238Sodium IodideHCID 78391,2-DibromoethaneHCID 14798Sodium HydroxideHCID 74952Bis(diphenylphosphino)methane

Product 1

HCID 303894Bis(diphenylphosphine)methane monooxide

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of palladium acetate (5 mg; 2.2×10-2 mmol), dppm (2.00 g; 5.21 mmol), 1,2-dibromoethane (2.0 g; 10.64 mmol), and dichloromethane (10 mL) was stirred for 20 minutes. To this solution, aqueous NaOH (20% by weight; 6 mL) containing NaI (40 mg; 0.27 mmol) was added and the mixture was vigorously stirred under reflux for 4 hours. The organic phase was filtered through a silica plug which was then washed with CH2Cl2 /AcOEt (3:1 by volume). The combined organic solutions were evaporated to dryness. The solid residue was dissolved in the minimum amount of boiling CH2Cl2, the warm solution was treated with ether (100 mL; portionwise) and left at room temperature for 2 hours. Slightly yellowish fluffy needles of spectroscopically and TLC pure dppmO were separated, washed with ether, and dried under vacuum. The yield was 1.53 g (74%). 1H NMR (CDCl3, 20° C.), δ: 3.1 (d, 2H, J=12.7 Hz, CH2); 7.1-7.9 (m, 20H, Ph). 31P NMR (CDCl3, 20° C.), δ: -26.5 (d, 1P, JP-P =50.5 Hz, PPh2); 29.8 (d, 1P, JP-P =50.5 Hz, P(O)Ph2).

Workup

  1. additionwas added
  2. stirringthe mixture was vigorously stirred
  3. temperatureunder reflux for 4 hours
  4. filtrationThe organic phase was filtered through a silica plug which
  5. washwas then washed with CH2Cl2 /AcOEt (3:1 by volume)
  6. customThe combined organic solutions were evaporated to dryness
  7. dissolutionThe solid residue was dissolved in the minimum amount of boiling CH2Cl2
  8. additionthe warm solution was treated with ether (100 mL
  9. waitportionwise) and left at room temperature for 2 hours
  10. customSlightly yellowish fluffy needles of spectroscopically and TLC pure dppmO were separated
  11. washwashed with ether
  12. customdried under vacuum

Sources & evidence

ORD record
ord-789bcb6607c249288db7e3cad7ad98e8
Source dataset
uspto-grants-1999_07
Patent number
US05919984

Reaction notes

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