Chlorobenzene → (Undec-10-en-1-yl)benzene

HRID 578606Notes

Reaction equation

HRID 578606 reaction equation
[C:1]1([Mg]Cl)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Mg].ClC1C=CC=CC=1.[CH2:17](Br)[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH:26]=[CH2:27].[Cl-].[NH4+]>O1CCCC1.[Cu]I>[C:1]1([CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH:18]=[CH2:17])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

8

Reactant 5

HCID 7964ChlorobenzeneHCID 25517Ammonium ChlorideHCID 28414811-Bromo-1-undeceneHCID 5462224MagnesiumHCID 178478979HCID 178478979, compound

Product 1

HCID 14433491(Undec-10-en-1-yl)benzeneYield 50%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
23 °C

Procedure

Commercial 25 wt. % phenyl magnesium chloride (0.4 mol) in tetrahydrofuran (Acros Organics, AcroSeal bottle) works as described in the following reaction and is transferred to a 250-mL Schlenk flask equipped with a magnetic stirrer, reflux condenser, nitrogen inlet, and rubber septum side arm via cannula under nitrogen. Alternatively, the Grignard is made as follows. A 250 mL, 3-necked flask equipped with a mechanical stirrer, reflux condenser, addition funnel and argon inlet is situated first in a cooled water bath and then later in an oil bath. Under nitrogen, magnesium (0.04 mol) is added to chlorobenzene (0.04 mol) in dry tetrahydrofuran (freshly distilled from sodium benzophenone ketyl, 20 g), and is vigorously stirred for 3 hours. Undecylenyl bromide (0.04 mol) is added, and then CuI (0.02 mol) is added. After refluxing for 24 hours followed by cooling to 23° C., ammonium chloride is added and the solvent is removed. Water is added and the mixture is extracted with methylene chloride. After drying the methylene chloride layer over sodium sulfate and then filtration, the solvent is removed to yield a white crystalline solid and a light-yellow oil. The oil is decanted from the white solid (biphenyl) and then distilled at 150° C. under high vacuum to obtain 11-phenylundecene in 50% yield. By-products which distill over between 23° C. and 150° C. include phenol, undecene, 11-chloroundecene, biphenyl and 11-bromoundecene. Still bottoms remaining after the 11-phenylundecene has distilled over include CH2═CH—(CH2)18—CH═CH2. Without copper(I) iodide, no reaction takes place after 3 days of continuous reflux under the conditions described.

Workup

  1. customas described in the following reaction
  2. customis transferred to a 250-mL Schlenk flask
  3. customequipped with a magnetic stirrer
  4. temperaturereflux condenser, nitrogen inlet
  5. customA 250 mL, 3-necked flask equipped with a mechanical stirrer
  6. temperaturereflux
  7. additioncondenser, addition funnel and argon inlet
  8. customis situated first in a cooled water bath
  9. distillationfreshly distilled from sodium benzophenone ketyl, 20 g), and
  10. temperatureAfter refluxing for 24 hours
  11. customthe solvent is removed
  12. additionWater is added
  13. extractionthe mixture is extracted with methylene chloride
  14. dry with materialAfter drying the methylene chloride layer over sodium sulfate
  15. filtrationfiltration
  16. customthe solvent is removed
  17. customto yield a white crystalline solid
  18. customThe oil is decanted from the white solid (biphenyl)
  19. distillationdistilled at 150° C. under high vacuum

Sources & evidence

ORD record
ord-337c46a5e80045cc93385352a491203f
Source dataset
uspto-grants-2015_05
Patent number
US09040596B2

Reaction notes

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