Water → 4-(5-bromopyridin-2-yl)-N,N-diphenylaniline

HRID 521540Notes

Reaction equation

HRID 521540 reaction equation
[C:1]1([N:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:8]2[CH:13]=[CH:12][C:11](B(O)O)=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Br:23][C:24]1[CH:25]=[CH:26][C:27](I)=[N:28][CH:29]=1.C([O-])([O-])=O.[Na+].[Na+].O>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.C1COCC1>[Br:23][C:24]1[CH:25]=[CH:26][C:27]([C:11]2[CH:12]=[CH:13][C:8]([N:7]([C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)=[CH:9][CH:10]=2)=[N:28][CH:29]=1

Participants

7

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 5936905-Bromo-2-iodopyridineHCID 121669344-(Diphenylamino)phenylboronic Acid (contains varying amounts of Anhydride)

Product 1

HCID 667995714-(5-bromopyridin-2-yl)-N,N-diphenylanilineYield 98.2%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-(diphenylamino)phenylboronic acid (7.00 g, 24.2 mmol), 5-bromo-2-iodopyridine (7.56 g, 26.6 mmol), tetrakis(triphenylphosphine)palladium(0) (1.40 g, 1.21 mmol), Na2CO3 (9.18 g, 86.6 mmol), H2O (84 mL) and THF (140 mL) was degassed with argon for about 1.5 hours (h) while stirring. The stirring reaction mixture was then maintained under argon at 80° C. for about 19 h. Upon confirming consumption of the starting material by thin layer chromatography (TLC) (SiO2, 19:1 hexanes-EtOAc), the reaction was cooled to room temperature (RT) and poured over EtOAc (500 mL). The organics were then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. The crude product was then purified via flash chromatography (SiO2, 2:1 hexanes-dichloromethane) to afford compound 1 (9.54 g, 98% yield) as a light yellow, crystalline solid.

Workup

  1. customwas degassed with argon for about 1.5 hours (h)
  2. customThe stirring reaction mixture
  3. customconsumption of the starting material by thin layer chromatography (TLC) (SiO2, 19:1 hexanes-EtOAc)
  4. temperaturethe reaction was cooled to room temperature (RT)
  5. additionpoured over EtOAc (500 mL)
  6. washThe organics were then washed with sat. NaHCO3, H2O and brine
  7. dry with materialdried over MgSO4
  8. filtrationfilter
  9. concentrationconcentrated in vacuo
  10. customThe crude product was then purified via flash chromatography (SiO2, 2:1 hexanes-dichloromethane)

Sources & evidence

ORD record
ord-041c17f4d33c4eb980baebae5886313e
Source dataset
uspto-grants-2016_05
Patent number
US09328086B2

Reaction notes

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