1,4-Dichlorobenzene → 1,4-Didodecylbenzene

HRID 2078756Notes

Reaction equation

HRID 2078756 reaction equation
[CH2:1]([Mg]Br)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].Cl[C:16]1[CH:21]=[CH:20][C:19](Cl)=[CH:18][CH:17]=1>CCOCC.Cl[Ni]1(Cl)[P](C2C=CC=CC=2)(C2C=CC=CC=2)CCC[P]1(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:1]([C:16]1[CH:21]=[CH:20][C:19]([CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][CH3:1])=[CH:18][CH:17]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

Participants

5

Reactant 2

HCID 46851,4-DichlorobenzeneHCID 178443215HCID 178443215, compound

Product 1

HCID 155972061,4-Didodecylbenzene

Reagents, catalysts & solvents 2

HCID 178418745HCID 178418745, compoundCatalystHCID 3283Diethyl EtherSolvent

Procedure

n-Dodecylmagnesium bromide (235 mL, 235.0 mmol, 1.0 M in diethyl ether) was added dropwise over 15 minutes, to a solution of 1,4-dichlorobenzene (15.00 g, 102.0 mmol) and [1,3-bis(diphenylphosphino)propane]nickel(II)chloride ((dppp)Cl2Ni, 70 mg) in dry ether (70 mL) at 0° C. The reaction mixture was subsequently allowed to warm to room temperature for about 30 minutes, heated under reflux for 1 day, and cooled to 0° C. again. The reaction was carefully quenched with water (10 mL) and HCl (70 mL, 2 M) and the aqueous layer was extracted with ether (2×50 mL). The combined organic layers were washed with water (30 mL), dried over MgSO4, and filtered. The solvent was then removed in vacuo and the crude product was heated to 100° C. under high vacuum (˜20 mtorr) for 10 hours to remove n-octane and n-octylbromide. 1,4-Di-n-dodecylbenzene (1) was obtained as a white solid (35.00 g, 83%). 1H NMR (CDCl3): δ 0.88 (t, 6H), 1.30 (m, 36H), 1.61 (m, 4H), 2.59 (t, 4H), 7.10 (s, 4H) ppm.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 1 day
  3. temperaturecooled to 0° C. again
  4. customThe reaction was carefully quenched with water (10 mL) and HCl (70 mL, 2 M)
  5. extractionthe aqueous layer was extracted with ether (2×50 mL)
  6. washThe combined organic layers were washed with water (30 mL)
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. customThe solvent was then removed in vacuo
  10. temperaturethe crude product was heated to 100° C. under high vacuum (˜20 mtorr) for 10 hours
  11. customto remove n-octane and n-octylbromide

Sources & evidence

ORD record
ord-1d7c254d46a24e879ad33ca8d5d4a395
Source dataset
uspto-grants-2011_04
Patent number
US07928249B2

Reaction notes

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