1,2-Dichlorobenzene → 1,2-Bis(2-ethylhexyl)benzene

HRID 2092930Notes

Reaction equation

HRID 2092930 reaction equation
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1Cl.[CH2:9]([CH:11]([CH2:15][CH2:16][CH2:17][CH3:18])[CH2:12][Mg]Br)[CH3:10]>Cl[Ni]1(Cl)[P](C2C=CC=CC=2)(C2C=CC=CC=2)CCC[P]1(C1C=CC=CC=1)C1C=CC=CC=1.CCOCC>[CH2:9]([CH:11]([CH2:15][CH2:16][CH2:17][CH3:18])[CH2:12][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:12][CH:11]([CH2:9][CH3:10])[CH2:15][CH2:16][CH2:17][CH3:18])[CH3:10]

Participants

5

Reactant 2

HCID 72391,2-DichlorobenzeneHCID 178443576HCID 178443576, compound

Product 1

HCID 159201171,2-Bis(2-ethylhexyl)benzeneYield 62%

Reagents, catalysts & solvents 2

HCID 178418745HCID 178418745, compoundCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
5 °C

Procedure

A dry 2 L 3-neck flask with attached reflux condenser and addition funnel, flushed with dry nitrogen, was charged with 1,2-dichlorobenzene (79.4 g, 540 mmol), Ni(dppp)Cl2 (3 g, 6 mmol), and 200 mL of dry Et2O. The addition funnel was charged with 2-ethylhexylmagnesium bromide (3M, 400 mL). The solution was cooled to 5° C. and the Grignard reagent was added dropwise to the reaction. After complete addition, the reaction was stirred at 5° C. for 30 min and then warmed to room temperature (RT). The reaction was then heated to reflux for 12 h. After cooling to RT, the reaction mixture was poured onto an ice/HCl (10%) solution and extracted with MTBE. The organic fractions were dried over anhydrous MgSO4 and then concentrated. The product was purified first by distillation followed by column chromatography with hexanes, and isolated as colorless oil (101 g, 62%).

Workup

  1. temperatureA dry 2 L 3-neck flask with attached reflux
  2. additioncondenser and addition funnel
  3. customflushed with dry nitrogen
  4. additionAfter complete addition
  5. temperaturewarmed to room temperature (RT)
  6. temperatureThe reaction was then heated
  7. temperatureto reflux for 12 h
  8. temperatureAfter cooling to RT
  9. extractionextracted with MTBE
  10. dry with materialThe organic fractions were dried over anhydrous MgSO4
  11. concentrationconcentrated
  12. distillationThe product was purified first by distillation

Sources & evidence

ORD record
ord-784f089103ee4d7bbc9bafffc6e47c30
Source dataset
uspto-grants-2013_05
Patent number
US08440785B2

Reaction notes

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