Pentane → 2,4-Bis(4-tert-butylphenyl)-6-[4-(5-phenylpyridin-2-yl)phenyl]-1,3,5-triazine

HRID 1671831Notes

Reaction equation

HRID 1671831 reaction equation
CCCCC.C([Li])(C)(C)C.O1CCCC1.Br[C:17]1[CH:22]=[CH:21][C:20]([C:23]2[N:28]=[C:27]([C:29]3[CH:34]=[CH:33][C:32]([C:35]([CH3:38])([CH3:37])[CH3:36])=[CH:31][CH:30]=3)[N:26]=[C:25]([C:39]3[CH:44]=[CH:43][C:42]([C:45]([CH3:48])([CH3:47])[CH3:46])=[CH:41][CH:40]=3)[N:24]=2)=[CH:19][CH:18]=1.Br[C:50]1[CH:55]=[CH:54][C:53]([C:56]2[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=2)=[CH:52][N:51]=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>[C:35]([C:32]1[CH:31]=[CH:30][C:29]([C:27]2[N:26]=[C:25]([C:39]3[CH:44]=[CH:43][C:42]([C:45]([CH3:47])([CH3:48])[CH3:46])=[CH:41][CH:40]=3)[N:24]=[C:23]([C:20]3[CH:19]=[CH:18][C:17]([C:50]4[CH:55]=[CH:54][C:53]([C:56]5[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=5)=[CH:52][N:51]=4)=[CH:22][CH:21]=3)[N:28]=2)=[CH:34][CH:33]=1)([CH3:36])([CH3:37])[CH3:38]

Participants

7

Reactant 5

HCID 8003PentaneHCID 8028Tetrahydrofuran3×HCID 27628752-Bromo-5-phenylpyridineHCID 594397872-(4-Bromophenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazineHCID 178418306HCID 178418306, compound

Product 1

HCID 673346992,4-Bis(4-tert-butylphenyl)-6-[4-(5-phenylpyridin-2-yl)phenyl]-1,3,5-triazineYield 91.4%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
-78 °C

Procedure

Under a stream of argon, 3.5 ml of a pentane solution containing 5.2 mmol of tert-butyl lithium was slowly added to 15 ml of tetrahydrofuran cooled to −78° C., and 10 ml of tetrahydrofuran in which 0.61 g of 2-bromo-5-phenylpyridine had been dissolved was further added dropwise to this solution. After stirring at −78° C. for 30 minutes, 1.64 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 35 ml portion of tetrahydrofuran prepared by dissolving 1.00 g of 2-(4-bromophenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine synthesized by the method of Reference Example 1 and 0.12 g of tetrakis(triphenylphosphine)palladium(0) therein was added to this solution and stirred under heating reflux for 10 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:dichloromethane=3:2 to 4:3) and then again recrystallized from dichloromethane-methanol to obtain a white solid of the intended 2,4-bis(4-tert-butylphenyl)-6-[4-(5-phenylpyridin-2-yl)phenyl]-1,3,5-triazine (1.05 g, yield 91%). Its melting point is shown in Table 4. In this case, a distinct point of glass transition was not observed.

Workup

  1. additionwas further added dropwise to this solution
  2. stirringstirred at −78° C. for 10 minutes
  3. waitat room temperature for 2 hours
  4. additiontherein was added to this solution
  5. stirringstirred
  6. temperatureunder heating
  7. temperaturereflux for 10 hours
  8. concentrationThe reaction solution was concentrated under a reduced pressure
  9. customthe thus obtained solid was recrystallized from dichloromethane-methanol
  10. customThe thus obtained crude product
  11. customwas purified by a silica gel column chromatography (eluting solution hexane:dichloromethane=3:2 to 4:3)
  12. customagain recrystallized from dichloromethane-methanol

Sources & evidence

ORD record
ord-61b87ffcc1974ca9925c6b1a7867db55
Source dataset
uspto-grants-2011_08
Patent number
US07994316B2

Reaction notes

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