Nitromethane → 4,4'-Bis(1,1-dimethylethyl)-1,1'-biphenyl

HRID 726912Notes

Reaction equation

HRID 726912 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].[C:5]1([C:11]2[CH:16]=CC=C[CH:12]=2)[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.C([C:21]1[CH:26]=[C:25](C)[CH:24]=[C:23]([C:28]([CH3:31])([CH3:30])[CH3:29])[C:22]=1O)(C)(C)C.[N+]([CH3:36])([O-])=O>>[C:11]([C:5]1[CH:6]=[CH:7][C:8]([C:26]2[CH:21]=[CH:22][C:23]([C:28]([CH3:29])([CH3:30])[CH3:31])=[CH:24][CH:25]=2)=[CH:9][CH:10]=1)([CH3:12])([CH3:16])[CH3:36]

Participants

5

Reactant 4

HCID 6375Nitromethane2×HCID 7095BiphenylHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 6451240Aluminum(III) Chloride

Product 1

HCID 741954,4'-Bis(1,1-dimethylethyl)-1,1'-biphenylYield 41%

Procedure

Into a 250 ml 3-neck round bottom flask equipped with a mechanical stirrer, thermometer, and inlet was charged, with agitation, 40 mL of nitromethane to which was added portionwise 20.7 grams (156 mmol, 1.69 eq) of aluminum chloride with agitation and cooling so as not to exceed 40° C. This solution was added to a mixture of 14.2 grams (92.1 mmol, 1.0 eq) of biphenyl and 26.5 grams (120 mmol, 1.3 eq) of 2,6-di-t-butyl-4-methylphenol in 40 mL of nitromethane at 15° C. over a period of 5 to 10 minutes. The mixture turned a dark opaque color and near the end of the addition, the mixture became very thick. The reaction mixture was allowed to stir for 30 minutes and then poured into ice-water. The mixture was extracted with ether twice and the ether layer was concentrated in vacuo. Additional ether was added to the solid and the mixture was concentrated in vacuo. Toluene was added to the solid and the mixture was concentrated in vacuo. This treatment was to insure removal of nitromethane before washing with base. The brown solid residue was dissolved in ether and washed with approximately 300 mL of 1M sodium hydroxide until the aqueous layer was no longer deeply colored. The organic layer was washed with water and concentrated in vacuo. The brown residue was recrystallized from approximately 150 mL of ethanol to give 10 grams (41% yield). Melting point=129°-130° C.

Workup

  1. customInto a 250 ml 3-neck round bottom flask equipped with a mechanical stirrer
  2. temperaturecooling so as not
  3. customto exceed 40° C
  4. additionnear the end of the addition
  5. extractionThe mixture was extracted with ether twice
  6. concentrationthe ether layer was concentrated in vacuo
  7. additionAdditional ether was added to the solid
  8. concentrationthe mixture was concentrated in vacuo
  9. additionToluene was added to the solid
  10. concentrationthe mixture was concentrated in vacuo
  11. customremoval of nitromethane
  12. washbefore washing with base
  13. dissolutionThe brown solid residue was dissolved in ether
  14. washwashed with approximately 300 mL of 1M sodium hydroxide until the aqueous layer
  15. washThe organic layer was washed with water
  16. concentrationconcentrated in vacuo
  17. customThe brown residue was recrystallized from approximately 150 mL of ethanol
  18. customto give 10 grams (41% yield)

Sources & evidence

ORD record
ord-f056bd12eb0a476c9e60901e047b5645
Source dataset
uspto-grants-1998_01
Patent number
US05710320

Reaction notes

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