4,4'-Dibromobiphenyl → HCID 20650340, compound

HRID 2206837Notes

Reaction equation

HRID 2206837 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-b691eb1fa7d1415cbaffe2d96f1919ee
Source dataset
uspto-grants-2016_06
Patent number
US09373797B2

Reaction notes

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