Potassium Carbonate → HCID 59609504, compound

HRID 468978Notes

Reaction equation

HRID 468978 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:7]=[C:8](Br)[CH:9]=1)[CH:5]=O.[C:11]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=1)(=O)[CH3:12].[I-].BrC1N=C(C(=O)C[N+:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)C=CC=1.BrC1N=[C:42]([C:44]2[CH:49]=[C:48]([C:50]3[CH:55]=[C:54](Br)[CH:53]=[C:52](Br)[CH:51]=3)[CH:47]=[C:46]([C:58]3[CH:63]=[CH:62][CH:61]=[CH:60]N=3)N=2)C=CC=1.[CH:64]1C2C3C=CC=CC=3NC=2C=CN=1.BrC1C=C(C2C=C(C3C=CC=CN=3)N=C(C3C=[CH:101][CH:100]=[C:99]([N:103]4C5C=CC=CC=5[C:105]5[CH:112]=[N:113][CH:114]=C[C:104]4=5)[N:98]=3)C=2)C=C(Br)C=1.C1(B(O)O)C=CC=CC=1.C(=O)([O-])[O-].[K+].[K+]>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(O)C.C1(C)C=CC=CC=1>[CH:114]1[C:5]2[C:4]3[CH:7]=[CH:8][CH:9]=[CH:2][C:3]=3[N:103]([C:99]3[N:98]=[C:11]([C:14]4[CH:19]=[C:18]([C:44]5[CH:42]=[C:46]([C:58]6[CH:63]=[CH:62][CH:61]=[CH:60][CH:64]=6)[CH:47]=[C:48]([C:50]6[CH:51]=[CH:52][CH:53]=[CH:54][CH:55]=6)[CH:49]=5)[CH:17]=[C:16]([C:35]5[CH:34]=[CH:33][CH:32]=[CH:31][N:30]=5)[N:15]=4)[CH:12]=[CH:101][CH:100]=3)[C:104]=2[CH:105]=[CH:112][N:113]=1

Participants

12

Reactant 8

HCID 11430Potassium CarbonateHCID 142862-AcetylpyridineHCID 66827Phenylboronic AcidHCID 130802gamma-CarbolineHCID 6220773,5-DibromobenzaldehydeHCID 12786936HCID 12786936, compoundHCID 68625142HCID 68625142, compound2×HCID 87519798HCID 87519798, compound

Product 1

HCID 59609504HCID 59609504, compoundYield 41%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Procedure

As in Example 4,3-(3,5-dibromophenyl)-1-(pyridin-2-yl)-propenone was synthesized from 3,5-dibromobenzaldehyde and 2-acetylpyridine, and further subjected to a reaction with [2-(6-bromopyridin-2-yl)oxoethyl]pyridinium iodide to synthesize 6-bromo-4′-(3,5-dibromophenyl)-[2,2′;6′,2″]terpyridine. This compound was further subjected to a reaction with 5H-pyrido[4,3-b]indole to synthesize 4′-(3,5-dibromophenyl)-6-(5H-pyrido[4,3-b]indol-5-yl)-[2,2′;6′,2″]terpyridine. To 5.1 g of the resulting 4′-(3,5-dibromophenyl)-6-(5H-pyrido[4,3-b]indol-5-yl)-[2,2′;6′,2″]terpyridine were added 2.1 g of phenylboronic acid, 0.5 g of tetrakis(triphenylphosphine)palladium, 20 mL of a 2 M aqueous potassium carbonate solution, 72 mL of toluene, and 18 mL of ethanol, followed by heating with reflux while stirring for 12 hours. After cooling to room temperature, the precipitate was collected by filtration. To the precipitate, 80 mL of chloroform was added and insoluble matter was removed by filtration. The filtrate was concentrated under a reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: toluene) and then recrystallized using o-dichlorobenzene. Thus, 2.1 g (yield, 41%) of 6-(5H-pyrido[4,3-b]indol-5-yl)-4′-[1,1′;3′,1″]terphenyl-5′-yl-[2,2′;6′,2″]terpyridine (Compound 136) was obtained as a white powder.

Workup

  1. temperatureby heating
  2. temperaturewith reflux
  3. filtrationthe precipitate was collected by filtration
  4. additionTo the precipitate, 80 mL of chloroform was added
  5. custominsoluble matter was removed by filtration
  6. concentrationThe filtrate was concentrated under a reduced pressure
  7. customto obtain a crude product
  8. customThe crude product was purified by column chromatography (carrier: NH silica gel, eluent: toluene)
  9. customrecrystallized

Sources & evidence

ORD record
ord-c6f85dd3e30f46f88c21ac365154872a
Source dataset
uspto-grants-2014_01
Patent number
US08624228B2

Reaction notes

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