1,2-Dibromoethane → [4-(Diphenylphosphanyl)butyl](oxo)diphenyl-lambda~5~-phosphane

HRID 581454Notes

Reaction equation

HRID 581454 reaction equation
[CH:1]1[CH:6]=[CH:5][C:4]([P:7]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[CH2:8][CH2:9][CH2:10][CH2:11][P:12]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:3][CH:2]=1.BrCCBr.[OH-:35].[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.ClCCl>[P:7]([CH2:8][CH2:9][CH2:10][CH2:11][P:12]([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)=[O:35])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:4]1[CH:3]=[CH:2][CH:1]=[CH:6][CH:5]=1

Participants

6

Reactant 3

HCID 78391,2-DibromoethaneHCID 14798Sodium HydroxideHCID 821241,4-Bis(diphenylphosphino)butane

Product 1

HCID 4392290[4-(Diphenylphosphanyl)butyl](oxo)diphenyl-lambda~5~-phosphane

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A mixture of palladium acetate (10 mg; 4.45×10-2 mmol), dppb (4.00 g; 9.4 mmol), 1,2-dibromoethane (3.6 g; 19.15 mmol), and dichloromethane (10 mL) was stirred for 30 minutes. To this suspension, aqueous NaOH (20% by weight; 10 mL) was added and the mixture was vigorously stirred at room temperature for 3 days. Dichloromethane (30 mL) was added, the organic phase was filtered through a silica plug which was then washed with 80 mL of CH2Cl2 /AcOEt (5:3 by volume). The combined organic solutions were evaporated to dryness. The solid residue was dissolved in boiling CH2Cl2 (ca. 30 mL) and the solution was treated with ether (100 mL; portionwise) and left at room temperature for 2 hours. Well-shaped, colorless crystals were separated, washed with ether, and dried under vacuum. The yield was 3.33 g (80%). 1H NMR (CDCl3, 20° C.), δ: 1.5 (m, 2H, CH2); 1.7 (m, 2H, CH2); 2.0 (m, 2H, CH2); 2.2 (m, 2H, CH2); 7.2-7.8 (m, 20H, Ph). 31P NMR (CDCl3, 20° C.), δ: -15.5 (s, 1P, PPh2); 32.2 (s, 1P, P(O)Ph2).

Workup

  1. stirringthe mixture was vigorously stirred at room temperature for 3 days
  2. filtrationthe organic phase was filtered through a silica plug which
  3. washwas then washed with 80 mL of CH2Cl2 /AcOEt (5:3 by volume)
  4. customThe combined organic solutions were evaporated to dryness
  5. dissolutionThe solid residue was dissolved
  6. additionthe solution was treated with ether (100 mL
  7. waitportionwise) and left at room temperature for 2 hours
  8. customWell-shaped, colorless crystals were separated
  9. washwashed with ether
  10. customdried under vacuum

Sources & evidence

ORD record
ord-21552b8f0eca4fcca247989035262044
Source dataset
uspto-grants-1999_07
Patent number
US05919984

Reaction notes

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