Tetrahydrofuran → 1,1-Bis(4-dimethylaminophenyl)-2-(dicyclohexylphosphino)propene

HRID 1282458Notes

Reaction equation

HRID 1282458 reaction equation
[CH3:1][N:2]([CH3:22])[C:3]1[CH:8]=[CH:7][C:6]([C:9]([C:13]2[CH:18]=[CH:17][C:16]([N:19]([CH3:21])[CH3:20])=[CH:15][CH:14]=2)=[C:10](Br)[CH3:11])=[CH:5][CH:4]=1.C1COCC1.C([Li])CCC.Cl[P:34]([CH:41]1[CH2:46][CH2:45][CH2:44][CH2:43][CH2:42]1)[CH:35]1[CH2:40][CH2:39][CH2:38][CH2:37][CH2:36]1>O>[CH3:1][N:2]([CH3:22])[C:3]1[CH:8]=[CH:7][C:6]([C:9]([C:13]2[CH:18]=[CH:17][C:16]([N:19]([CH3:21])[CH3:20])=[CH:15][CH:14]=2)=[C:10]([P:34]([CH:41]2[CH2:42][CH2:43][CH2:44][CH2:45][CH2:46]2)[CH:35]2[CH2:40][CH2:39][CH2:38][CH2:37][CH2:36]2)[CH3:11])=[CH:5][CH:4]=1

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 2734135ChlorodicyclohexylphosphineHCID 184244981,1-Bis(4-dimethylaminophenyl)-2-bromopropeneHCID 178418339Butyllithium

Product 1

HCID 120108271,1-Bis(4-dimethylaminophenyl)-2-(dicyclohexylphosphino)propeneYield 23.1%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
-60 °C

Procedure

Into a reactor were introduced 1.44 g (4.00 mmol) of the 1,1-bis(4-dimethylaminophenyl)-2-bromopropene obtained in Example 4 (2) and 14 mL of THF under a nitrogen atmosphere. The contents were cooled to −60° C. Thereto was gradually added dropwise 2.8 mL (4.4 mmol; 1.6 M hexane solution) of butyllithium. The resultant mixture was stirred at that temperature for 1 hour. Thereafter, 0.97 mL (4.4 mmol) of chlorodicyclohexylphosphine was added thereto, and this mixture was stirred for 30 minutes, subsequently heated to room temperature, and then further stirred for 17 hours. Water was added to the reaction mixture. The organic layer was extracted with ethyl acetate, and the extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was recrystallized from ethanol and hexane to obtain 0.44 g (23%) of the target compound as white crystals.

Workup

  1. temperaturesubsequently heated to room temperature
  2. stirringfurther stirred for 17 hours
  3. extractionThe organic layer was extracted with ethyl acetate
  4. dry with materialthe extract was dried with anhydrous magnesium sulfate
  5. customThereafter, the solvent was removed under reduced pressure
  6. customThe concentrate was recrystallized from ethanol and hexane

Sources & evidence

ORD record
ord-8875edbf8d70480ebd5f2290c33b9127
Source dataset
uspto-grants-2002_09
Patent number
US06455720B1

Reaction notes

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