1,4-Dichlorobenzene → 1,4-Didodecylbenzene

HRID 1257974Notes

Reaction equation

HRID 1257974 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-b2218badfd1e401e8a20fdaf47f9a2f6
Source dataset
uspto-grants-2013_06
Patent number
USRE044304E1

Reaction notes

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