Acetone → 4,7-bis(4-phenoxyphenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

HRID 1050683Notes

Reaction equation

HRID 1050683 reaction equation
Br[C:2]1[C:10]2[C:6](=[N:7][N:8]([C:11]3[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=3)[N:9]=2)[C:5](Br)=[CH:4][CH:3]=1.[O:18]([C:25]1[CH:30]=[CH:29][C:28](B(O)O)=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[C:34](=[O:37])([O-])[O-].[Na+].[Na+].[CH3:40][C:41]([CH3:43])=O>O.C(O)CCC.C1(C)C=CC=CC=1.ClCCl.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>[O:18]([C:25]1[CH:30]=[CH:29][C:28]([C:2]2[C:10]3[C:6](=[N:7][N:8]([C:11]4[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=4)[N:9]=3)[C:5]([C:41]3[CH:43]=[CH:16][C:11]([O:37][C:34]4[CH:6]=[CH:10][CH:2]=[CH:3][CH:4]=4)=[CH:12][CH:40]=3)=[CH:4][CH:3]=2)=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

10

Reactant 4

HCID 180AcetoneHCID 10340Sodium CarbonateHCID 27343774-Phenoxyphenylboronic acidHCID 866799014,7-dibromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799064,7-bis(4-phenoxyphenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Reagents, catalysts & solvents 5

HCID 178418397HCID 178418397, compoundCatalystHCID 2631-ButanolSolventHCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of Intermediate A (704 mg, 2 mmol), 4-phenoxyphenylboronic acid (2.14 g, 10 mmol), tetrakis(triphenylphosphine)palladium (0) (0.50 g, 0.43 mmol), sodium carbonate (2.12 g, 20 mmol) in water (8 mL), n-butanol (20 mL), toluene (20 mL), and acetone (5 mL) is heated under argon at 110° C. for 16 hours. The reaction mixture is poured into water (100 mL), diluted with dichloromethane (100 mL), stirred for 1 hour, and the dichloromethane layer is separated. The aqueous phase is washed with dichloromethane (100 mL). Both dichloromethane solutions are combined, dried over anhydrous sodium sulfate, and the solvent is removed under reduced pressure. The crude product is purified by column chromatography (silica gel, dichloromethane/ethyl acetate 9:1) and recrystallization from ethyl acetate to give 4,7-bis(4-phenoxyphenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (Example 2), yellow-green crystals, 865 mg (81%). 1H NMR (400 MHz, CDCl3): δ 8.82 (m, 2H, pyridine), 8.35 (m, 2H, pyridine), 8.12 (d, J=8.7 Hz, 4H, p-phenylene), 7.69 (s, 2H, benzotriazole), 7.40 (m, 4H, Ph), 7.18 (d, J=8.7 Hz, 4H, p-phenylene), 7.17 (m, 2H, Ph), 7.13 (m, 4H, Ph). UV-vis spectrum (dichloromethane): λmax=386 nm. Fluorimetry (dichloromethane): λmax=499 nm.

Workup

  1. customthe dichloromethane layer is separated
  2. washThe aqueous phase is washed with dichloromethane (100 mL)
  3. dry with materialdried over anhydrous sodium sulfate
  4. customthe solvent is removed under reduced pressure
  5. customThe crude product is purified by column chromatography (silica gel, dichloromethane/ethyl acetate 9:1) and recrystallization from ethyl acetate

Sources & evidence

ORD record
ord-da7d8af7e750434aa0f2e12528c6ace1
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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