Sodium Carbonate → 4-bromo-7-(4-(pyren-1-yl)phenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

HRID 1050695Notes

Reaction equation

HRID 1050695 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:17])=[CH:4][CH:3]=1.[C:18]1(B(O)O)[C:31]2[C:32]3=[C:33]4[C:28](=[CH:29][CH:30]=2)[CH:27]=[CH:26][CH:25]=[C:24]4[CH:23]=[CH:22][C:21]3=[CH:20][CH:19]=1.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>O.C(O)CCC.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.C1(C)C=CC=CC=1>[Br:17][C:5]1[C:6]2[C:10](=[N:9][N:8]([C:11]3[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=3)[N:7]=2)[C:2]([C:18]2[CH:31]=[CH:30][C:29]([C:28]3[C:33]4[C:24]5=[C:23]6[C:22](=[CH:21][CH:32]=4)[CH:5]=[CH:4][CH:3]=[C:2]6[CH:10]=[CH:6][C:25]5=[CH:26][CH:27]=3)=[CH:20][CH:19]=2)=[CH:3][CH:4]=1

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 5084102Pyren-1-ylboronic acidHCID 866799014,7-dibromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799174-bromo-7-(4-(pyren-1-yl)phenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazoleYield 58.9%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 2631-ButanolSolventHCID 962WaterSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of Intermediate A (1.41 g, 4 mmol), pyrene-1-boronic acid (0.49 g, 2.0 mmol), tetrakis(triphenylphosphine)palladium (0) (0.50 g, 0.43 mmol), sodium carbonate (2.12 g, 20 mmol) in water (10 mL), n-butanol (30 mL), and toluene (30 mL) was heated under argon at 110° C. for 5 hours. The reaction mixture was poured into water (200 mL), treated with 5 N NaOH (20 mL), stirred for 1 hour, and extracted with dichloromethane (2×200 mL). The extract was dried over anhydrous sodium carbonate, and the volatiles were removed under reduced pressure. The residue was chromatographed (silica gel, dichloromethane/tetrahydrofuran 9:10) to give 4-bromo-7-(4-(pyren-1-yl)phenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (purity 90%, 650 mg, 53% yield) as yellow crystals. 1H NMR (400 MHz, CDCl3): δ 8.72 (m, 2H, pyridine), 8.31 (d, J=7.7 Hz, 1H, pyrene), 8.24 (dd, J=7.7 and 1.1 Hz, 1H, pyrene), 8.16-8.20 (m, 6H, pyrene and pyridine), 8.04 (t, J=7.7 Hz, 1H, pyrene), 8.00 (m, 2H, pyrene), 7.86 (d, J=7.7 Hz, 1H, benzotriazole), 7.86 (d, J=7.3 Hz, 1H, benzotriazole).

Workup

  1. extractionextracted with dichloromethane (2×200 mL)
  2. dry with materialThe extract was dried over anhydrous sodium carbonate
  3. customthe volatiles were removed under reduced pressure
  4. customThe residue was chromatographed (silica gel, dichloromethane/tetrahydrofuran 9:10)

Sources & evidence

ORD record
ord-5dc27f7253b042afaafdb2a688f3ee7b
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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