Water → 4,4'-(3,3'-bipyridine-6,6'-diyl)bis(N,N-diphenylaniline)

HRID 521541Notes

Reaction equation

HRID 521541 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH:26]=[CH:25][C:11]([N:12]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)=[CH:10][CH:9]=2)=[N:6][CH:7]=1.[C:27]1([N:33]([C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=2)[C:34]2[CH:39]=[CH:38][C:37]([C:40]3[CH:45]=[CH:44][C:43](B4OC(C)(C)C(C)(C)O4)=[CH:42][N:41]=3)=[CH:36][CH:35]=2)[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=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>[N:6]1[C:5]([C:8]2[CH:26]=[CH:25][C:11]([N:12]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)=[CH:10][CH:9]=2)=[CH:4][CH:3]=[C:2]([C:43]2[CH:42]=[N:41][C:40]([C:37]3[CH:38]=[CH:39][C:34]([N:33]([C:55]4[CH:56]=[CH:57][CH:58]=[CH:59][CH:60]=4)[C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)=[CH:35][CH:36]=3)=[CH:45][CH:44]=2)[CH:7]=1

Participants

7

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 667995714-(5-bromopyridin-2-yl)-N,N-diphenylanilineHCID 66801665N,N-diphenyl-4-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)aniline

Product 1

HCID 569437294,4'-(3,3'-bipyridine-6,6'-diyl)bis(N,N-diphenylaniline)Yield 82%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1 (3.05 g, 7.59 mmol), 2 (3.40 g, 7.59 mmol), tetrakis(triphenylphosphine)palladium(0) (0.438 g, 0.379 mmol), Na2CO3 (7.42 g, 70.0 mmol), H2O (70 mL) and THF (115 mL) was degassed with argon for about 1.25 h while stirring. The stirring reaction mixture was then maintained under argon at 80° C. for about 65 h. Upon confirming consumption of the starting materials by TLC (SiO2, CH2Cl2), the reaction was cooled to room temperature (RT) and poured over CH2Cl2 (400 mL). The organics were then washed with sat. NaHCO3, H2O and brine, dried over MgSO4, filter and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 100% CH2Cl2 to 49:1 CH2Cl2-acetone) provided 3 (3.98 g, 82% yield) as a yellow solid.

Workup

  1. customwas degassed with argon for about 1.25 h
  2. customThe stirring reaction mixture
  3. customconsumption of the starting materials by TLC (SiO2, CH2Cl2)
  4. temperaturethe reaction was cooled to room temperature (RT)
  5. additionpoured over CH2Cl2 (400 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. customPurification of the crude product via flash chromatography (SiO2, 100% CH2Cl2 to 49:1 CH2Cl2-acetone)

Sources & evidence

ORD record
ord-96680b552ae745bdbabc0883f47086a8
Source dataset
uspto-grants-2016_05
Patent number
US09328086B2

Reaction notes

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