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

HRID 1050685Notes

Reaction equation

HRID 1050685 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.[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.CO[C:39]1[CH:44]=[CH:43][C:42](B(O)O)=[CH:41][CH:40]=1.C(=O)([O-])[O-].[Na+].[Na+]>O.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.C(O)CCC>[C:18]1([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:39]3[C:44]4[C:43]5=[C:32]6[C:31](=[CH:30][CH:29]=4)[CH:18]=[CH:19][CH:20]=[C:21]6[CH:22]=[CH:23][C:42]5=[CH:41][CH:40]=3)=[CH:4][CH:3]=2)[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

Participants

9

Reactant 4

HCID 10340Sodium CarbonateHCID 201262(4-Methoxyphenyl)boronic acidHCID 5084102Pyren-1-ylboronic acidHCID 866799014,7-dibromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799084,7-di(pyren-1-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazoleYield 40.9%

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 (1.23 g, 5.0 mmol), 4-methoxyphenylboronic acid (0.76 g, 5.0 mmol), sodium carbonate (2.12 g, 20 mmol) in water (10 mL), tetrakis(triphenylphosphine)palladium (0) (0.50 g, 0.43 mmol), n-butanol (30 mL), and toluene (20 mL) was heated under argon at 110° C. for 4 hours. Thin layer chromatography (TLC) of the reaction mixture indicated no starting material left. The reaction mixture was poured into water (200 mL) and extracted with dichloromethane (3×200 mL). The extract was dried over anhydrous sodium carbonate, and the volatiles were removed under reduced pressure. The residue was chromatographed (silica gel, dichloromethane/ethyl acetate 95:5). The first fraction gave 4,7-di(pyren-1-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (Example 4) (610 mg, 25%) as orange crystals. 1H NMR (400 MHz, CDCl3): δ 8.60 (m, 2H, pyridine), 8.38 (m, 4H, pyrene), 8.22-8.29 (m, 6H, pyrene), 8.20 (m, 4H, pyrene), 8.05-8.10 (m, 6H, pyrene and pyridine), 7.90 (s, 2H, benzotriazole). UV-vis spectrum (dichloromethane): λmax=381 nm. Fluorimetry (dichloromethane): λmax=524 nm.

Workup

  1. waitleft
  2. extractionextracted with dichloromethane (3×200 mL)
  3. dry with materialThe extract was dried over anhydrous sodium carbonate
  4. customthe volatiles were removed under reduced pressure
  5. customThe residue was chromatographed (silica gel, dichloromethane/ethyl acetate 95:5)

Sources & evidence

ORD record
ord-dfd56be40db847d7a34b1a00f5aa6609
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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