Toluene → 2,2'-[2,2'-Bipyridine-5,6-diylbis(biphenyl-4,4'-diyl)]bisbenzoxazole

HRID 1097169Notes

Reaction equation

HRID 1097169 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:9]=[CH:10][C:11]([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][N:22]=3)=[N:12][C:13]=2[C:14]2[CH:19]=[CH:18][C:17](Br)=[CH:16][CH:15]=2)=[CH:4][CH:3]=1.[C:27](=[O:30])([O-])[O-].[Na+].[Na+].[O:33]1[C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][C:36]=2[N:35]=[C:34]1[C:42]1[CH:47]=[CH:46][C:45](B(O)O)=[CH:44][CH:43]=1.[C:51]1([CH3:57])[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=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.CO.O.C(O)C>[N:12]1[C:13]([C:14]2[CH:15]=[CH:16][C:17]([C:45]3[CH:46]=[CH:47][C:42]([C:34]4[O:33][C:37]5[CH:38]=[CH:39][CH:40]=[CH:41][C:36]=5[N:35]=4)=[CH:43][CH:44]=3)=[CH:18][CH:19]=2)=[C:8]([C:5]2[CH:6]=[CH:7][C:2]([C:54]3[CH:55]=[CH:56][C:51]([C:57]4[O:30][C:27]5[CH:5]=[CH:8][CH:9]=[CH:10][C:11]=5[N:12]=4)=[CH:52][CH:53]=3)=[CH:3][CH:4]=2)[CH:9]=[CH:10][C:11]=1[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][N:22]=1

Participants

9

Reactant 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 579585085,6-Bis(4-bromophenyl)-2,2'-bipyridineHCID 57958561(4-(Benzo[d]oxazol-2-yl)phenyl)boronic acid

Product 1

HCID 579585262,2'-[2,2'-Bipyridine-5,6-diylbis(biphenyl-4,4'-diyl)]bisbenzoxazoleYield 54%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

Into a 100 mL three-neck flask were put 1.4 g (3.0 mmol) of 5,6-bis(4-bromophenyl)-2,2′-bipyridine, 1.3 g (12 mmol) of sodium carbonate, 1.6 g (6.6 mmol) of 4-(benzoxazol-2-yl)phenylboronic acid, 25 ml of toluene, 6 ml of ethanol, 6 ml of water. The mixture was degassed by being stirred under reduced pressure, and the atmosphere in the flask was substituted by nitrogen. 0.14 g (0.12 mmol) of tetrakis(triphenylphosphine)palladium(0) was added, and the mixture was stirred at 80° C. for 11 hours under a nitrogen stream. After a certain time, the mixture was cooled to room temperature, and the precipitated solid was recovered by suction filtration. The obtained solid was dissolved in chloroform, and washed with water and saturated saline, then the organic layer was dried over magnesium sulfate. The obtained mixture was subjected to gravity filtration, and the obtained filtrate was concentrated to give a solid. A toluene solution of the obtained solid was subjected to suction filtration through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The filtrate was condensed to give a solid. A suspension in which methanol was added to this solid was irradiated with ultrasonic waves, and subjected to suction filtration to recover the solid. Then, the solid was recrystallized with toluene, so that 1.1 g of a target substance, white powder was recovered in a yield of 54%.

Workup

  1. customInto a 100 mL three-neck flask were put
  2. customThe mixture was degassed
  3. stirringthe mixture was stirred at 80° C. for 11 hours under a nitrogen stream
  4. filtrationthe precipitated solid was recovered by suction filtration
  5. dissolutionThe obtained solid was dissolved in chloroform
  6. washwashed with water and saturated saline
  7. dry with materialthe organic layer was dried over magnesium sulfate
  8. filtrationThe obtained mixture was subjected to gravity filtration
  9. concentrationthe obtained filtrate was concentrated
  10. customto give a solid
  11. filtrationA toluene solution of the obtained solid was subjected to suction filtration through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855)
  12. customcondensed
  13. customto give a solid
  14. customwas irradiated with ultrasonic waves
  15. filtrationsubjected to suction filtration
  16. customto recover the solid
  17. customThen, the solid was recrystallized with toluene, so that 1.1 g of a target substance, white powder
  18. customwas recovered in a yield of 54%

Sources & evidence

ORD record
ord-79301d271d9f4823ab501d6a7a5a0e95
Source dataset
uspto-grants-2012_03
Patent number
US08142911B2

Reaction notes

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