Dichloromethane → [3-(Diphenylphosphanyl)propyl](oxo)diphenyl-lambda~5~-phosphane

HRID 581453Notes

Reaction equation

HRID 581453 reaction equation
[CH:1]1[CH:2]=[CH:3][C:4]([P:7]([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[CH2:8][CH2:9][CH2:10][P:11]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[CH:5][CH:6]=1.BrCCBr.[OH-:34].[Na+].C(Cl)Cl>ClCCCl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CCCCC.CCOCC>[P:7]([CH2:8][CH2:9][CH2:10][P:11]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)=[O:34])([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:4]1[CH:3]=[CH:2][CH:1]=[CH:6][CH:5]=1

Participants

9

Reactant 4

HCID 6344DichloromethaneHCID 78391,2-DibromoethaneHCID 14798Sodium HydroxideHCID 812191,3-Bis(diphenylphosphino)propane

Product 1

HCID 3336369[3-(Diphenylphosphanyl)propyl](oxo)diphenyl-lambda~5~-phosphane

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 111,2-DichloroethaneSolventHCID 3283Diethyl EtherSolventHCID 8003PentaneSolvent2×

Procedure

Palladium acetate (10 mg; 4.45×10-2 mmol), dppp (5.00 g; 12.14 mmol), and 1,2-dibromoethane (3.4 g; 18.9 mmol) were dissolved in 1,2-dichloroethane (15 mL). To this solution, aqueous NaOH (20% by weight; 10 mL) was added and the biphasic mixture was vigorously stirred under reflux for 6 hours until the originally yellow mixture turned pale yellow. The organic phase was filtered through a silica column which was then washed with CH2Cl2 /AcOEt (5:3 by volume) until the yellow band was about to come out. The combined organic solutions were evaporated to give a colorless oily residue. The oil was mixed with CH2Cl2 (2 mL) and ether (5 mL), and then treated with pentane (10 mL) and left for 1.5 hours. More pentane (50 ml) was added, and in 2 hours the fluffy white needles of dpppO were separated and dried under vacuum. The yield was 3.80 g (73%). 1H NMR (CDCl3, 20° C.), δ: 1.8 (m, 2H, CH2); 2.2 (m, 2H, CH2); 2.4 (m, 2H, CH2); 7.2-7.7 (m, 20H, Ph). 31P NMR (CDCl3, 20° C.), δ: -17.2 (s, 1P, PPh2); 32.0 (s, 1P, P(O)Ph2).

Workup

  1. temperatureunder reflux for 6 hours until the originally yellow mixture
  2. filtrationThe organic phase was filtered through a silica column which
  3. washwas then washed with CH2Cl2 /AcOEt (5:3 by volume) until the yellow band
  4. customThe combined organic solutions were evaporated
  5. customto give a colorless oily residue
  6. customin 2 hours the fluffy white needles of dpppO were separated
  7. customdried under vacuum

Sources & evidence

ORD record
ord-8f6af12a08ad46deb152294c38c5d79b
Source dataset
uspto-grants-1999_07
Patent number
US05919984

Reaction notes

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