Ammonium Chloride → 2,2'-Bis(diisobutylphosphinomethyl)-1,1'-biphenyl

HRID 1200290

Reaktionsgleichung

Reaktionsgleichung von HRID 1200290
[CH2:1]([PH:5][CH2:6][CH:7]([CH3:9])[CH3:8])[CH:2]([CH3:4])[CH3:3].C([Li])[CH2:11][CH2:12][CH3:13].Br[CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[CH2:29]Br.[NH4+].[Cl-]>C1COCC1.CCCCCC.C(OCC)C>[CH2:1]([P:5]([CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[CH2:29][P:5]([CH2:6][CH:12]([CH3:11])[CH3:13])[CH2:1][CH:2]([CH3:4])[CH3:3])[CH2:6][CH:7]([CH3:9])[CH3:8])[CH:2]([CH3:4])[CH3:3]

Komponenten

8

Edukt 4

HCID 25517Ammonium ChlorideHCID 77622Phosphine, bis(2-methylpropyl)-HCID 2519622,2'-Bis(bromomethyl)-1,1'-biphenylHCID 178418339Butyllithium

Produkt 1

HCID 139550462,2'-Bis(diisobutylphosphinomethyl)-1,1'-biphenylAusbeute 72 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

Diisobutylphosphine (1.66 grams, 11.37 mmol) was dissolved in THF (25 ml) under nitrogen and cooled with a dry ice/acetone bath. n-Butyllithium (7.11 ml of a 1.6M solution in hexane, 11.37 mmol) was added dropwise to the stirring solution which was then allowed to stir for 1 hour in the cold bath. 2,2'-Bis(bromomethyl)-1,1'-biphenyl (1.89 grams, 5.55 mmol) in THF (10 ml) was added dropwise at -70° C. The solution was allowed to stir overnight at room temperature and was then heated at reflux for 1 hour. Saturated aqueous NH4Cl was added to the solution at room temperature. Diethyl ether was added and the layers were separated in a separatory funnel. The aqueous layer was extracted twice with diethyl ether, and the combined organic solution was then washed twice with water. The solvent was removed on a steam bath under a stream of nitrogen. The oily residue was then placed on a Kugelrohr distillation apparatus to remove low boiling material at about 175° C. and 1 mm Hg leaving 1.88 grams (72% yield) of a thick orange glassy product. 1H NMR (CDCl3): δ 0.65-1.67 (complex, 36H, aliphatic); 2.42 (s, 4H, benzylic); 6.67-7.30 (complex, 8H aromatic). 31P NMR (CDCl3): δ+31.

Aufarbeitung

  1. temperaturecooled with a dry ice/acetone bath
  2. stirringto stir overnight at room temperature
  3. temperaturewas then heated
  4. temperatureat reflux for 1 hour
  5. customthe layers were separated in a separatory funnel
  6. extractionThe aqueous layer was extracted twice with diethyl ether
  7. washthe combined organic solution was then washed twice with water
  8. customThe solvent was removed on a steam bath under a stream of nitrogen
  9. distillationThe oily residue was then placed on a Kugelrohr distillation apparatus
  10. customto remove low boiling material at about 175° C.

Quellen und Nachweise

ORD-Eintrag
ord-934d7d685ac6477ebb2cd03de74524d6
Quelldatensatz
uspto-grants-1990_02
Patentnummer
US04904808

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