Tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane → 4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

HRID 1050688Notes

Reaction equation

HRID 1050688 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([Sn](CCCC)(CCCC)[C:23]1[S:24][CH:25]=[C:26]2[C:31]=1[O:30][CH2:29][CH2:28][O:27]2)CCC>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>[O:27]1[CH2:28][CH2:29][O:30][C:31]2=[C:23]([C:2]3[C:10]4[C:6](=[N:7][N:8]([C:11]5[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=5)[N:9]=4)[C:5]([C:25]4[S:24][CH:23]=[C:31]5[C:26]=4[O:27][CH2:28][CH2:29][O:30]5)=[CH:4][CH:3]=3)[S:24][CH:25]=[C:26]12

Participants

5

Reactant 2

HCID 15891053Tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannaneHCID 866799014,7-dibromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799104,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of Intermediate A (0.71 g, 2.0 mmol), tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane (2.27 g, 5.0 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.20 g, 0.28 mmol), and anhydrous dimethylformamide (20 mL) was stirred under argon and heated at 100° C. for 4 hours. The volatiles were removed under reduced pressure, and the crude product was purified by column chromatography (silica gel, dichloromethane/ethyl acetate 75:25) and washing with ethanol (20 mL) to give 4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (Example 10) as orange crystals, 0.47 g (49%). 1H NMR (400 MHz, CDCl3): δ 8.82 (m, 2H, pyridine), 8.37 (m, 2H, pyridine), 8.20 (s, 2H, benzotriazole), 6.53 (s, 2H, thiophene), 4.39 (s, 4H, OCH2CH2O), 4.30 (s, 4H, OCH2CH2O). UV-vis spectrum (dichloromethane): λmax=448 nm. Fluorimetry (dichloromethane): λmax=559 nm.

Workup

  1. customThe volatiles were removed under reduced pressure
  2. customthe crude product was purified by column chromatography (silica gel, dichloromethane/ethyl acetate 75:25)
  3. washwashing with ethanol (20 mL)

Sources & evidence

ORD record
ord-bbe9350ed19149a1ac76f7f6d9049290
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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