Hexane → 5-{4-[4,6-Bis(4-biphenylyl)-1,3,5-triazin-2-yl]phenyl}-2,4'-bipyridyl

HRID 1671840Notes

Reaction equation

HRID 1671840 reaction equation
CCCCCC.C([Li])CCC.[C:12]1([C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[CH:17]=[CH:16][C:15]([C:18]2[N:23]=[C:22]([C:24]3[CH:29]=[CH:28][C:27]([C:30]4[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=4)=[CH:26][CH:25]=3)[N:21]=[C:20]([C:36]3[CH:41]=[CH:40][C:39](Br)=[CH:38][CH:37]=3)[N:19]=2)=[CH:14][CH:13]=1.Br[C:50]1[CH:51]=[CH:52][C:53]([C:56]2[CH:61]=[CH:60][N:59]=[CH:58][CH:57]=2)=[N:54][CH:55]=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:12]1([C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[CH:17]=[CH:16][C:15]([C:18]2[N:23]=[C:22]([C:24]3[CH:29]=[CH:28][C:27]([C:30]4[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=4)=[CH:26][CH:25]=3)[N:21]=[C:20]([C:36]3[CH:41]=[CH:40][C:39]([C:50]4[CH:51]=[CH:52][C:53]([C:56]5[CH:61]=[CH:60][N:59]=[CH:58][CH:57]=5)=[N:54][CH:55]=4)=[CH:38][CH:37]=3)[N:19]=2)=[CH:14][CH:13]=1

Participants

7

Reactant 4

HCID 8058HexaneHCID 116587125-Bromo-2,4'-bipyridineHCID 673352762,4-Bisbiphenyl-4-yl-6-(4-bromophenyl)-1,3,5-triazineHCID 178418339Butyllithium

Product 1

HCID 673347885-{4-[4,6-Bis(4-biphenylyl)-1,3,5-triazin-2-yl]phenyl}-2,4'-bipyridylYield 54.2%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Under a stream of argon, 2.2 ml of a hexane solution containing 3.3 mmol of butyl lithium was slowly added to 60 ml of tetrahydrofuran cooled to −78° C. in which 1.62 g of 2,4-bis(4-biphenylyl)-6-(4-bromophenyl)-1,3,5-triazine obtained in Reference Example 3 had been dissolved. After stirring at −78° C. for 15 minutes, 0.91 g of dichloro(tetramethylethylenediamine)zinc(II) was added thereto and stirred at −78° C. for 10 minutes and then at room temperature for 2 hours. A 30 ml portion of tetrahydrofuran prepared by dissolving 0.71 g of 5-bromo-2,4′-bipyridyl and 0.14 g of tetrakis(triphenylphosphine)palladium(0) therein was added to this solution and stirred under heating reflux for 14 hours. The reaction solution was concentrated under a reduced pressure and the thus obtained solid was recrystallized from dichloromethane-methanol. The thus obtained crude product was purified by a silica gel column chromatography (eluting solution hexane:chloroform=2:1 to chloroform) and an alumina gel column chromatography (eluting solution hexane:chloroform=1:1) and then recrystallized from dichloromethane-methanol to obtain a white solid of the intended 5-{4-[4,6-bis(4-biphenylyl)-1,3,5-triazin-2-yl]phenyl}-2,4′-bipyridyl (1.00 g, yield 54%).

Workup

  1. customobtained in Reference Example 3
  2. dissolutionhad been dissolved
  3. stirringstirred at −78° C. for 10 minutes
  4. waitat room temperature for 2 hours
  5. additiontherein was added to this solution
  6. stirringstirred
  7. temperatureunder heating
  8. temperaturereflux for 14 hours
  9. concentrationThe reaction solution was concentrated under a reduced pressure
  10. customthe thus obtained solid was recrystallized from dichloromethane-methanol
  11. customThe thus obtained crude product
  12. customwas purified by a silica gel column chromatography (eluting solution hexane:chloroform=2:1 to chloroform)
  13. washan alumina gel column chromatography (eluting solution hexane:chloroform=1:1)
  14. customrecrystallized from dichloromethane-methanol

Sources & evidence

ORD record
ord-e7e774128f7345dab5145a1d86c8e757
Source dataset
uspto-grants-2011_08
Patent number
US07994316B2

Reaction notes

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