Diphenylphosphine → Nmdpp

HRID 1604751

Reaction equation

HRID 1604751 reaction equation
[C:1]1([PH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Li])CCC.[CH:19]1([CH3:29])[CH2:24][CH2:23][CH:22]([CH:25]([CH3:27])[CH3:26])[CH:21](Cl)[CH2:20]1>O1CCCC1>[CH3:29][C@@H:19]1[CH2:20][C@@H:21]([P:7]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C@@H:22]([CH:25]([CH3:27])[CH3:26])[CH2:23][CH2:24]1

Participants

5

Reactant 3

HCID 70017DiphenylphosphineHCID 859512-Chloro-4-methyl-1-(1-methylethyl)cyclohexaneHCID 178418339Butyllithium

Product 1

HCID 12665338NmdppYield 54.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

Diphenylphosphine (140 g, 0.75 mol) was charged into a 2-L, 3-neck, round-bottom flask in a glove box under a nitrogen atmosphere. The reactor was connected to a nitrogen manifold. Freshly distilled tetrahydrofuran (400 mL) was added to the mixture and the mixture was cooled to -20° C. Normal butyllithium (1.6 M in hexanes, 468 mL, 0.75 mol) was added over a 2 hour period. The cold bath was removed and the orange solution was warmed to room temperature. After stirring at room temperature for 0.5 hour, (-)-menthyl chloride (129 g, 0.74 mol) was added. The mixture was stirred at room temperature for 21 hours and then heated at reflux for 40 hours. The reaction mixture was cooled to room temperature and quenched with H2O (125 mL). After stirring for 2 hours, the organic layer was separated, washed with H2O (125 mL) and concentrated to an oil. The resulting material was distilled under vacuum until crystal formation was observed in the distillation condenser to give about 130 g of crude NMDPP in the pot.

Workup

  1. customThe cold bath was removed
  2. temperaturethe orange solution was warmed to room temperature
  3. stirringThe mixture was stirred at room temperature for 21 hours
  4. temperatureheated
  5. temperatureat reflux for 40 hours
  6. temperatureThe reaction mixture was cooled to room temperature
  7. customquenched with H2O (125 mL)
  8. stirringAfter stirring for 2 hours
  9. customthe organic layer was separated
  10. washwashed with H2O (125 mL)
  11. concentrationconcentrated to an oil
  12. distillationThe resulting material was distilled under vacuum until crystal formation

Sources & evidence

ORD record
ord-2f82544475b74aa2b8f9bca6bec8bd1a
Source dataset
uspto-grants-1999_11
Patent number
US05994587

Linked notes

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