Ammonium Chloride → Diphenyl-1-pyrenylphosphine

HRID 1967660Notes

Reaction equation

HRID 1967660 reaction equation
Br[C: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-].[C:24]1([PH:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.[NH4+].[Cl-]>C1COCC1>[C:31]1([P:30]([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C:2]2[C:15]3[C:16]4=[C:17]5[C:12](=[CH:13][CH:14]=3)[CH:11]=[CH:10][CH:9]=[C:8]5[CH:7]=[CH:6][C:5]4=[CH:4][CH:3]=2)[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 1596271-BromopyreneHCID 19695023Diphenylphosphane chlorideHCID 178418339Butyllithium

Product 1

HCID 130626Diphenyl-1-pyrenylphosphineYield 39%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

Bromopyrene (5 mmol, 1.41 g) was charged and dissolved in THF (25 ml). After the solution was cooled to −78° C., n-BuLi (5.5 mmol, 2.08 ml, 2.64 M, 1.1 eq) was slowly added dropwise to the solution and the mixture was stirred for 2 hours. Then, diphenylphosphine chloride (5 mmol, 0.92 ml, 1 eq) was slowly added dropwise to the mixture, followed by stirring overnight. Saturated NH4Cl (10 mL) was added to the mixture. The THF layer was separated from the aqueous layer. The aqueous layer was extracted with dichloromethane (50 mL×3). The organic layer and the THF layer were combined. The resulting mixture was dried over sodium sulfate and concentrated on an evaporator. The residue was purified by silica gel column chromatography (developing solvent: dichloromethane:hexane=1:3). Thus, diphenylpyrenylphosphine (DPPP) was obtained (yield 39%) as white yellow crystals. The crystals were identified by 1H-NMR and 31P-NMR.

Workup

  1. stirringby stirring overnight
  2. customThe THF layer was separated from the aqueous layer
  3. extractionThe aqueous layer was extracted with dichloromethane (50 mL×3)
  4. dry with materialThe resulting mixture was dried over sodium sulfate
  5. concentrationconcentrated on an evaporator
  6. customThe residue was purified by silica gel column chromatography (developing solvent: dichloromethane:hexane=1:3)

Sources & evidence

ORD record
ord-a90da806970b4625b31867a4209b94d5
Source dataset
uspto-grants-2013_04
Patent number
US08420865B2

Reaction notes

Loading…