Pentane → 2,4-Bis(4-tert-butylphenyl)-6-[4'-(2-pyridyl)biphenyl-4-yl]-1,3,5-triazine

HRID 1671830Notes

Reaction equation

HRID 1671830 reaction equation
CCCCC.C([Li])(C)(C)C.Br[C:12]1[CH:17]=[CH:16][C:15]([C:18]2[N:23]=[C:22]([C:24]3[CH:29]=[CH:28][C:27]([C:30]([CH3:33])([CH3:32])[CH3:31])=[CH:26][CH:25]=3)[N:21]=[C:20]([C:34]3[CH:39]=[CH:38][C:37]([C:40]([CH3:43])([CH3:42])[CH3:41])=[CH:36][CH:35]=3)[N:19]=2)=[CH:14][CH:13]=1.Br[C:45]1[CH:50]=[CH:49][C:48]([C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][N:52]=2)=[CH:47][CH:46]=1>O1CCCC1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:40]([C:37]1[CH:38]=[CH:39][C:34]([C:20]2[N:21]=[C:22]([C:24]3[CH:29]=[CH:28][C:27]([C:30]([CH3:33])([CH3:31])[CH3:32])=[CH:26][CH:25]=3)[N:23]=[C:18]([C:15]3[CH:14]=[CH:13][C:12]([C:45]4[CH:46]=[CH:47][C:48]([C:51]5[CH:56]=[CH:55][CH:54]=[CH:53][N:52]=5)=[CH:49][CH:50]=4)=[CH:17][CH:16]=3)[N:19]=2)=[CH:35][CH:36]=1)([CH3:43])([CH3:42])[CH3:41]

Participants

7

Reactant 4

HCID 8003PentaneHCID 15152372-(4-Bromophenyl)pyridineHCID 594397872-(4-Bromophenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazineHCID 178418306HCID 178418306, compound

Product 1

HCID 673362722,4-Bis(4-tert-butylphenyl)-6-[4'-(2-pyridyl)biphenyl-4-yl]-1,3,5-triazineYield 87%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolvent3×

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-(4-bromophenyl)pyridine was 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 1.00 g portion of 2-(4-bromophenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine prepared in Reference Example 1 and 0.12 g of tetrakis(triphenylphosphine) palladium(0) were dissolved in 35 ml of tetrahydrofuran and added to this solution, followed by stirring under heating reflux for 13 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′-(2-pyridyl)biphenyl-4-yl]-1,3,5-triazine (1.00 g, yield 87%). Its melting point and glass transition temperature are shown in Table 4.

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. additionadded to this solution
  5. stirringby stirring
  6. temperatureunder heating
  7. temperaturereflux for 13 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-1015ed01d1b7473ba892de7e330e69ec
Source dataset
uspto-grants-2011_08
Patent number
US07994316B2

Reaction notes

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