Phenyl phosphorus dichloride → 4-Methoxyphenylphenylpyrenylphosphine

HRID 1967656Notes

Reaction equation

HRID 1967656 reaction equation
[Br-].[CH:2]1[C:15]2[C:16]3=[C:17]4[C:12](=[CH:13][CH:14]=2)[CH:11]=[CH:10][CH:9]=[C:8]4[CH:7]=[CH:6][C:5]3=[CH:4][CH:3]=1.[Li]CCCC.Cl[P:24](Cl)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.[CH3:32][O:33][C:34]1[CH:39]=[CH:38][C:37]([Mg]Br)=[CH:36][CH:35]=1.[H][H]>C1COCC1>[CH3:32][O:33][C:34]1[CH:39]=[CH:38][C:37]([P:24]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:9]2[C:8]3[C:17]4=[C:16]5[C:5](=[CH:6][CH:7]=3)[CH:4]=[CH:3][CH:2]=[C:15]5[CH:14]=[CH:13][C:12]4=[CH:11][CH:10]=2)=[CH:36][CH:35]=1

Participants

7

Reactant 5

HCID 12573Phenyl phosphorus dichlorideHCID 86650098Pyrene bromideHCID 178418339ButyllithiumHCID 178418361HCID 178418361, compoundHCID 178491912HCID 178491912, compound

Product 1

HCID 541970834-MethoxyphenylphenylpyrenylphosphineYield 32%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Pyrene bromide [IIa] (3.28 g, 15 mmol) was dissolved in 70 mL of THF, and n-BuLi (6.11 mL, 2.7 M, 16.5 mmol, 1.1 eq) was added dropwise to the solution at −78° C. over 15 minutes. The mixture was stirred for 3 hours. This reaction product was dropwise added over 15 minutes to dichlorophenylphosphine [IIIa] (2.03 mL, 15 mmol, 1 eq) dissolved in 6 mL of THF (−78° C.). After stirring overnight, 4-methoxyphenyl magnesium bromide [IVa] (45 mL, 0.5 M, 22.5 mmol, 1.5 eq) was dropwise added over 15 minutes to the reaction mixture at −78° C. After stirring the mixture for 6 hours, the reaction was quenched with 50 mL of saturated ammonium chloride aqueous solution. The inorganic salt produced was removed by suction filtration, followed by extraction with dichloromethane (100 mL×3). The organic layer was dried over sodium sulfate and concentrated on an evaporator. The residue was purified by column chromatography using a developing solvent (dichloromethane:hexane=1:2). The product was obtained as pale yellow crystals in 32% yield. The pale yellow crystals were identified by 1H-NMR, 31P-NMR, 13C-NMR, H—H COSY and C—H COSY.

Workup

  1. stirringAfter stirring overnight
  2. stirringAfter stirring the mixture for 6 hours
  3. customthe reaction was quenched with 50 mL of saturated ammonium chloride aqueous solution
  4. customThe inorganic salt produced
  5. customwas removed by suction filtration
  6. extractionfollowed by extraction with dichloromethane (100 mL×3)
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. concentrationconcentrated on an evaporator
  9. customThe residue was purified by column chromatography
  10. customThe product was obtained as pale yellow crystals in 32% yield

Sources & evidence

ORD record
ord-f4aa3afc21d644fa9b7bcddfac116b81
Source dataset
uspto-grants-2013_04
Patent number
US08420865B2

Reaction notes

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