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

HRID 1671833Notes

Reaction equation

HRID 1671833 reaction equation
CCCCCC.C([Li])CCC.Br[C:13]1[CH:18]=[CH:17][C:16]([C:19]2[N:24]=[C:23]([C:25]3[CH:30]=[CH:29][C:28]([C:31]([CH3:34])([CH3:33])[CH3:32])=[CH:27][CH:26]=3)[N:22]=[C:21]([C:35]3[CH:40]=[CH:39][C:38]([C:41]([CH3:44])([CH3:43])[CH3:42])=[CH:37][CH:36]=3)[N:20]=2)=[CH:15][CH:14]=1.Br[C:46]1[N:51]=[C:50]([C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][N:53]=2)[CH:49]=[CH:48][CH:47]=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:31]([C:28]1[CH:27]=[CH:26][C:25]([C:23]2[N:22]=[C:21]([C:35]3[CH:40]=[CH:39][C:38]([C:41]([CH3:43])([CH3:44])[CH3:42])=[CH:37][CH:36]=3)[N:20]=[C:19]([C:16]3[CH:15]=[CH:14][C:13]([C:46]4[N:51]=[C:50]([C:52]5[CH:57]=[CH:56][CH:55]=[CH:54][N:53]=5)[CH:49]=[CH:48][CH:47]=4)=[CH:18][CH:17]=3)[N:24]=2)=[CH:30][CH:29]=1)([CH3:32])([CH3:33])[CH3:34]

Participants

7

Reactant 4

HCID 8058HexaneHCID 117911522-Bromo-6-(pyridin-2-yl)pyridineHCID 594397872-(4-Bromophenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazineHCID 178418339Butyllithium

Product 1

HCID 673351346-{4-[4,6-Bis(4-tert-butylphenyl)-1,3,5-triazin-2-yl]phenyl}-2,2'-bipyridylYield 71.3%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Under a stream of argon, 1.4 ml of a hexane solution containing 2.2 mmol of butyl lithium was slowly added to 40 ml of tetrahydrofuran cooled to −78° C. in which 1.00 g of 2-(4-bromophenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine obtained in Reference Example 1 had been dissolved. After stirring at −78° C. for 15 minutes, 0.61 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 20 ml portion of tetrahydrofuran prepared by dissolving 0.56 g of 6-bromo-2,2′-bipyridyl and 0.12 g of tetrakis(triphenylphosphine)palladium(0) therein was added to this solution and stirred under heating reflux for 20 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 (developing solvent hexane:chloroform=1:1 to 0:1) and then again recrystallized from dichloromethane-methanol to obtain a white solid of the intended 6-{4-[4,6-bis(4-tert-butylphenyl)-1,3,5-triazin-2-yl]phenyl}-2,2′-bipyridyl (0.82 g, yield 71%). Its melting point and glass transition temperature are shown in Table 4.

Workup

  1. customobtained in Reference Example 1
  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 20 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 (developing solvent hexane:chloroform=1:1 to 0:1)
  13. customagain recrystallized from dichloromethane-methanol

Sources & evidence

ORD record
ord-eb8baa67f253464dadeda2c8002c7e1e
Source dataset
uspto-grants-2011_08
Patent number
US07994316B2

Reaction notes

Loading…