Dimethyl Ether → 2'-amino-p-terphenyl

HRID 2041817Notes

Reaction equation

HRID 2041817 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:6](Br)=[CH:5][C:3]=1[NH2:4].[C:10]1(B(O)O)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.C(=O)([O-])[O-].[Na+].[Na+].COC>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[C:10]1([C:2]2[CH:8]=[CH:7][C:6]([C:2]3[CH:8]=[CH:7][CH:6]=[CH:5][CH:3]=3)=[CH:5][C:3]=2[NH2:4])[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

7

Reactant 4

HCID 8254Dimethyl EtherHCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 771982,5-Dibromoaniline

Product 1

HCID 125954862'-amino-p-terphenylYield 81%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Procedure

2,5-dibromoaniline (50 g, 199.27 mmol, 1.0 equivalent), phenylboronic acid (58.31 g, 478.25 mmol, 2.4 equivalents), tetrakis(triphenylphosphine)palladium(0) (6.91 g, 5.98 mmol, 0.03 equivalent), sodium carbonate (238.48 g), dimethyl ether (750 milliliters), and water (750 milliliters) were loaded, and the mixture was refluxed for 7 hours. After that, the precipitate was separated by filtration and removed, and ethyl acetate was added to the resultant reaction solution so that an organic layer was extracted. The extracted organic layer was washed with a saturated salt solution, dried with anhydrous sodium sulfate, and concentrated. The resultant residue was purified by short column chromatography (methylene chloride) and silica gel chromatography (methylene chloride:hexane=1:1→2:1). An appropriate amount of hexane was added to the purified residue, and the resultant precipitate was separated by filtration. The resultant precipitate was dried, whereby a white solid was obtained (39.4 g, yield: 81%).

Workup

  1. temperaturethe mixture was refluxed for 7 hours
  2. customAfter that, the precipitate was separated by filtration
  3. customremoved
  4. additionethyl acetate was added to the resultant
  5. customreaction solution so that an organic layer
  6. extractionwas extracted
  7. washThe extracted organic layer was washed with a saturated salt solution
  8. dry with materialdried with anhydrous sodium sulfate
  9. concentrationconcentrated
  10. customThe resultant residue was purified by short column chromatography (methylene chloride) and silica gel chromatography (methylene chloride:hexane=1:1→2:1)
  11. additionAn appropriate amount of hexane was added to the purified residue
  12. customthe resultant precipitate was separated by filtration
  13. dry with materialThe resultant precipitate was dried
  14. customwhereby a white solid was obtained (39.4 g, yield: 81%)

Sources & evidence

ORD record
ord-3d0472208fb9404f8a86c70833955554
Source dataset
uspto-grants-2013_11
Patent number
US08586199B2

Reaction notes

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