Hexane → 6-[4-(4,6-Di-m-tolyl-1,3,5-triazin-2-yl)phenyl]-2,2'-bipyridyl

HRID 1671836Notes

Reaction equation

HRID 1671836 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:26]=[C:27]([CH3:31])[CH:28]=[CH:29][CH:30]=3)[N:22]=[C:21]([C:32]3[CH:33]=[C:34]([CH3:38])[CH:35]=[CH:36][CH:37]=3)[N:20]=2)=[CH:15][CH:14]=1.Br[C:40]1[N:45]=[C:44]([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][N:47]=2)[CH:43]=[CH:42][CH:41]=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:27]1([CH3:31])[CH:28]=[CH:29][CH:30]=[C:25]([C:23]2[N:22]=[C:21]([C:32]3[CH:33]=[C:34]([CH3:38])[CH:35]=[CH:36][CH:37]=3)[N:20]=[C:19]([C:16]3[CH:15]=[CH:14][C:13]([C:40]4[N:45]=[C:44]([C:46]5[CH:51]=[CH:50][CH:49]=[CH:48][N:47]=5)[CH:43]=[CH:42][CH:41]=4)=[CH:18][CH:17]=3)[N:24]=2)[CH:26]=1

Participants

7

Reactant 4

HCID 8058HexaneHCID 117911522-Bromo-6-(pyridin-2-yl)pyridineHCID 673367582-(4-Bromophenyl)-4,6-di-m-tolyl-1,3,5-triazineHCID 178418339Butyllithium

Product 1

HCID 673346626-[4-(4,6-Di-m-tolyl-1,3,5-triazin-2-yl)phenyl]-2,2'-bipyridylYield 61%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Under a stream of argon, 2.1 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 1.25 g of 2-(4-bromophenyl)-4,6-di-m-tolyl-1,3,5-triazine obtained in Reference Example 2 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 20 ml portion of tetrahydrofuran prepared by dissolving 0.85 g of 6-bromo-2,2′-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 (developing solvent hexane:chloroform=1:1 to 1:2) and then again recrystallized from dichloromethane-methanol to obtain a white solid of the intended 6-[4-(4,6-di-m-tolyl-1,3,5-triazin-2-yl)phenyl]-2,2′-bipyridyl (0.89 g, yield 61%). Its melting point is shown in Table 4. In this case, a distinct point of glass transition was not observed.

Workup

  1. customobtained in Reference Example 2
  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 (developing solvent hexane:chloroform=1:1 to 1:2)
  13. customagain recrystallized from dichloromethane-methanol

Sources & evidence

ORD record
ord-c880f767cec947e1952458bededf5e40
Source dataset
uspto-grants-2011_08
Patent number
US07994316B2

Reaction notes

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