Pentane → 2-{4-[5-(4-Tert-butylphenyl)pyridin-2-yl]phenyl}-4,6-di-m-tolyl-1,3,5-triazine

HRID 1671832Notes

Reaction equation

HRID 1671832 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:30]=[C:31]([CH3:35])[CH:32]=[CH:33][CH:34]=3)[N:26]=[C:25]([C:36]3[CH:37]=[C:38]([CH3:42])[CH:39]=[CH:40][CH:41]=3)[N:24]=2)=[CH:19][CH:18]=1.Br[C:44]1[CH:49]=[CH:48][C:47]([C:50]2[CH:55]=[CH:54][C:53]([C:56]([CH3:59])([CH3:58])[CH3:57])=[CH:52][CH:51]=2)=[CH:46][N:45]=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:56]([C:53]1[CH:54]=[CH:55][C:50]([C:47]2[CH:48]=[CH:49][C:44]([C:17]3[CH:18]=[CH:19][C:20]([C:23]4[N:24]=[C:25]([C:36]5[CH:37]=[C:38]([CH3:42])[CH:39]=[CH:40][CH:41]=5)[N:26]=[C:27]([C:29]5[CH:30]=[C:31]([CH3:35])[CH:32]=[CH:33][CH:34]=5)[N:28]=4)=[CH:21][CH:22]=3)=[N:45][CH:46]=2)=[CH:51][CH:52]=1)([CH3:59])([CH3:58])[CH3:57]

Participants

7

Reactant 5

HCID 8003PentaneHCID 8028Tetrahydrofuran3×HCID 457887592-Bromo-5-(4-tert-butylphenyl)pyridineHCID 673367582-(4-Bromophenyl)-4,6-di-m-tolyl-1,3,5-triazineHCID 178418306HCID 178418306, compound

Product 1

HCID 673347892-{4-[5-(4-Tert-butylphenyl)pyridin-2-yl]phenyl}-4,6-di-m-tolyl-1,3,5-triazineYield 94.4%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
-78 °C

Procedure

Under a stream of argon, 5.3 ml of a pentane solution containing 7.8 mmol of tert-butyl lithium was slowly added to 25 ml of tetrahydrofuran cooled to −78° C., and 15 ml of tetrahydrofuran in which 1.13 g of 2-bromo-5-(4-tert-butylphenyl)pyridine had been dissolved was further added dropwise to this solution. After stirring at −78° C. for 30 minutes, 2.47 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 50 ml portion of tetrahydrofuran prepared by dissolving 1.25 g of 2-(4-bromophenyl)-4,6-di-m-tolyl-1,3,5-triazine synthesized by the method of Reference Example 2 and 0.17 g of tetrakis(triphenylphosphine)palladium(0) therein was added to this solution and stirred under heating reflux for 3 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-[5-(4-tert-butylphenyl)pyridin-2-yl]phenyl}-4,6-di-m-tolyl-1,3,5-triazine (1.55 g, yield 94%). 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 3 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-0e33f005101647b7a95366e9e4f11464
Source dataset
uspto-grants-2011_08
Patent number
US07994316B2

Reaction notes

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