Stannane, [2,2'-bithiophen]-5-yltributyl- → 4,7-di([2,2'-bithiophen]-5-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

HRID 1050686Notes

Reaction equation

HRID 1050686 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.[S:18]1[C:22]([Sn](CCCC)(CCCC)CCCC)=[CH:21][CH:20]=[C:19]1[C:36]1[S:37][CH:38]=[CH:39][CH:40]=1>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CN(C)C=O>[S:37]1[C:38]([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:22]3[S:18][C:19]([C:36]4[S:37][CH:38]=[CH:39][CH:40]=4)=[CH:20][CH:21]=3)=[CH:4][CH:3]=2)=[CH:39][CH:40]=[C:36]1[C:19]1[S:18][CH:22]=[CH:21][CH:20]=1

Participants

5

Reactant 2

HCID 11201877Stannane, [2,2'-bithiophen]-5-yltributyl-HCID 866799014,7-dibromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799094,7-di([2,2'-bithiophen]-5-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of Intermediate A (704 mg, 2.0 mmol), 50% [2,2′-bithiophen]-5-yltributylstannane (2.50 g, 5.5 mmol), bis(triphenylphosphine)palladium(II) dichloride (200 mg, 0.28 mmol), and anhydrous dimethylformamide (20 mL) was stirred under argon and heated at 90° C. for 1 hour. TLC indicated no starting material left. Heating at 90° C. was continued for an additional 2 hours. The volatiles were removed under reduced pressure, and the crude product was purified by column chromatography using silica gel and dichloromethane/ethyl acetate (9:1) as an eluent. The obtained product was washed with ethyl acetate (50 mL) and dried in a vacuum oven to give 4,7-di([2,2′-bithiophen]-5-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (Example 9) as red crystals, 150 mg (14%). 1H NMR (400 MHz, CDCl3): δ 8.88 (m, 2H, pyridine), 8.40 (m, 2H, pyridine), 8.09 (d, J=4.0 Hz, 2H, thiophene), 7.65 (s, 2H, benzotriazole), 7.31 (dd, J=3.7 and 1.1 Hz, 2H, thiophene), 7.29 (m, 2H, thiophene), 7.27 (m, 2H, thiophene), 7.08 (dd, J=5.2 and 3.7 Hz, 2H, thiophene). UV-vis spectrum (dichloromethane): λmax=478 nm. Fluorimetry (dichloromethane): λmax=584 nm.

Workup

  1. waitleft
  2. temperatureHeating at 90° C.
  3. customThe volatiles were removed under reduced pressure
  4. customthe crude product was purified by column chromatography
  5. washThe obtained product was washed with ethyl acetate (50 mL)
  6. customdried in a vacuum oven

Sources & evidence

ORD record
ord-215d45f373b74ed4bf1f50e6db6c096d
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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