2-Bromo-6-phenylpyridine → HCID 58526502, compound

HRID 1190244Notes

Reaction equation

HRID 1190244 reaction equation
[C:1]([Li])([CH3:4])([CH3:3])[CH3:2].Br[C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[N:8]=1.Br[C:20]1[CH:21]=[C:22]([C:32]2[N:37]=[C:36]([C:38]3[CH:39]=[C:40]([C:45]4[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=4)[CH:41]=[C:42](Br)[CH:43]=3)[N:35]=[C:34]([C:51]3[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=3)[N:33]=2)[CH:23]=[C:24]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:25]=1>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.O1CCCC1>[C:13]1([C:9]2[N:8]=[C:7]([C:20]3[CH:21]=[C:22]([C:32]4[N:37]=[C:36]([C:38]5[CH:39]=[C:40]([C:45]6[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=6)[CH:41]=[C:42]([C:7]6[CH:12]=[CH:11][CH:10]=[C:2]([C:1]7[CH:4]=[CH:14][CH:13]=[CH:9][CH:3]=7)[N:8]=6)[CH:43]=5)[N:35]=[C:34]([C:51]5[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=5)[N:33]=4)[CH:23]=[C:24]([C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[CH:25]=3)[CH:12]=[CH:11][CH:10]=2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

6

Reactant 3

HCID 5686792-Bromo-6-phenylpyridineHCID 58526490HCID 58526490, compoundHCID 178418306HCID 178418306, compound2×

Product 1

HCID 58526502HCID 58526502, compoundYield 52%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent5×

Conditions

Temperature
-78 °C

Procedure

In a stream of argon, tetrahydrofuran (3 mL) was cooled to −78° C. To the cooled tetrahydrofuran, a tetrahydrofuran solution (1.18 mL) of tert-butyllithium (1.58 mol/L) was added. Then a tetrahydrofuran solution (2 mL) of 2-bromo-6-phenylpyridine (211 mg) was dropwise added to the tert-butyllithium solution. The mixture was stirred for 15 minutes while the mixture was maintained at −78° C. To the reaction mixture, zinc chloride tetramethylethylenediamine complex (530 mg) was added to allow the temperature to rise naturally to room temperature. Then, to the reaction mixture, a tetrahydrofuran suspension (2 mL) having suspended therein 2,4-bis(5-bromobiphenyl-3-yl)-6-phenyl-1,3,5-triazine (185.8 mg) and tetrakis(triphenylphosphine)palladium (13.9 mg) was dropwise added. The resultant mixture was stirred at 50° C. for 19 hours. The reaction mixture was left to stand at room temperature, and then low-boiling ingredients were distilled away under a reduced pressure. Methanol was added, and the solid precipitate was recovered by filtration. The obtained crude product was purified by silica gel chromatography using a hexane/chloroform (2:1) mixed liquid as a developing solvent, to give 120 mg of the target 2,4-bis[5-(6-phenylpyridin-2-yl)biphenyl-3-yl]-6-phenyl-1,3,5-triazine as a white powder (yield: 52%).

Workup

  1. additionTo the reaction mixture, zinc chloride tetramethylethylenediamine complex (530 mg) was added
  2. customto rise naturally to room temperature
  3. waitThe reaction mixture was left
  4. customto stand at room temperature
  5. distillationlow-boiling ingredients were distilled away under a reduced pressure
  6. additionMethanol was added
  7. filtrationthe solid precipitate was recovered by filtration
  8. customThe obtained crude product
  9. customwas purified by silica gel chromatography
  10. additionmixed liquid as a developing solvent

Sources & evidence

ORD record
ord-ef83dccee47845ce87cd2012492ca315
Source dataset
uspto-grants-2014_03
Patent number
US08674091B2

Reaction notes

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