4,4'-Dibromobiphenyl → HCID 20650340, compound

HRID 1968380Notes

Reaction equation

HRID 1968380 reaction equation
[C:1]1([CH3:15])[CH:6]=[CH:5][C:4]([NH:7][C:8]2[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=2)=[CH:3][CH:2]=1.Br[C:17]1[CH:22]=[CH:21][C:20]([C:23]2[CH:28]=[CH:27][C:26]([Br:29])=[CH:25][CH:24]=2)=[CH:19][CH:18]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1>[Br:29][C:26]1[CH:27]=[CH:28][C:23]([C:20]2[CH:21]=[CH:22][C:17]([N:7]([C:8]3[CH:9]=[CH:10][C:11]([CH3:14])=[CH:12][CH:13]=3)[C:4]3[CH:3]=[CH:2][C:1]([CH3:15])=[CH:6][CH:5]=3)=[CH:18][CH:19]=2)=[CH:24][CH:25]=1

Participants

5

Reactant 3

HCID 71104,4'-DibromobiphenylHCID 69293Benzenamine, 4-methyl-N-(4-methylphenyl)-HCID 23676156Sodium t-butoxide

Product 1

HCID 20650340HCID 20650340, compoundYield 72.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

Di-p-tolylamine (6.0 g, 30.4 mmol), 4,4′-dibromobiphenyl (23.7 g, 76.0 mmol), sodium tert-butoxide (7.26 g, 91.2 mmol), and [1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (Pd(dppf)Cl2) (666 mg, 0.912 mmol, 3 mol %) were added to anhydrous toluene (about 250 ml) and degassed in argon for about 30 minutes. The resulting mixture was heated to about 80° C. for about 6 hours, after which a TLC analysis indicated that most of the di-p-tolylamine was consumed. After being cooled to RT, the mixture was poured into saturated aqueous sodium bicarbonate and extracted with 2 portions of ethyl acetate. The organic layers were pooled and washed with water and brine, then dried over MgSO4. After filtration the extract was concentrated to dryness on a rotary evaporator, then loaded onto silica gel. A flash column (gradient of 100% hexane to 1% methylene chloride in hexane) resulted in 9.4 g (72%) of a white solid Compound 7 confirmed by 1H NMR in CDCl3.

Workup

  1. customdegassed in argon for about 30 minutes
  2. customwas consumed
  3. temperatureAfter being cooled to RT
  4. additionthe mixture was poured into saturated aqueous sodium bicarbonate
  5. extractionextracted with 2 portions of ethyl acetate
  6. washwashed with water and brine
  7. dry with materialdried over MgSO4
  8. filtrationAfter filtration the extract
  9. concentrationwas concentrated to dryness on a rotary evaporator

Sources & evidence

ORD record
ord-a19459d617ba41dfb6783927b3b3017a
Source dataset
uspto-grants-2013_04
Patent number
US08426040B2

Reaction notes

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