Dimethylformamide → HCID 86679916, compound

HRID 1050694Notes

Reaction equation

HRID 1050694 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([NH:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C(=O)([O-])[O-].[K+].[K+].[CH3:37][N:38]([CH3:41])C=O>[Cu]I.O>[C:25]1([N:24]([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]([N:38]([C:41]3[CH:15]=[CH:16][CH:11]=[CH:12][CH:13]=3)[C:37]3[CH:6]=[CH:10][CH:2]=[CH:3][CH:4]=3)=[CH:4][CH:3]=2)[C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 11487DiphenylamineHCID 866799014,7-dibromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 86679916HCID 86679916, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolvent

Conditions

Temperature
160 °C

Procedure

A mixture of Intermediate A (1.05 g, 3.0 mmol), diphenylamine (2.03 g, 12.0 mmol), potassium carbonate (1.66 g, 12.0 mmol), CuI (1.14 g, 6.0 mmol), and dimethylformamide (20 mL) was stirred under argon and heated at 160° C. for 3 days. After cooling, the reaction mixture was poured into water (100 mL) and stirred for 15 minutes. The precipitate was filtered off and washed with water (50 mL). A suspension of this solid in dichloromethane (100 mL) was treated with concentrated ammonium hydroxide (20 mL) and stirred for 1 hour. The dichloromethane layer was separated, dried over sodium sulfate and chromatographed (silica gel, dichloromethane/ethyl acetate 9:1). The obtained product was recrystallized from ethanol to give 4,7-bis(N,N-diphenylamino)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (Example 19), orange crystals, 55 mg (3%). 1H NMR (400 MHz, CDCl3): δ 8.57 (m, 2H, pyridine), 7.64 (m, 2H, pyridine), 7.28 (m, 8H, Ph), 7.15 (m, 8H, Ph), 7.06 (t, J=7.3 Hz, 4H, Ph), 6.96 (s, 2H, benzotriazole. UV-vis spectrum (dichloromethane): λmax=471 nm. Fluorimetry (dichloromethane): λmax=640 nm.

Workup

  1. temperatureAfter cooling
  2. stirringstirred for 15 minutes
  3. filtrationThe precipitate was filtered off
  4. washwashed with water (50 mL)
  5. additionA suspension of this solid in dichloromethane (100 mL)
  6. additionwas treated with concentrated ammonium hydroxide (20 mL)
  7. stirringstirred for 1 hour
  8. customThe dichloromethane layer was separated
  9. dry with materialdried over sodium sulfate
  10. customchromatographed (silica gel, dichloromethane/ethyl acetate 9:1)
  11. customThe obtained product was recrystallized from ethanol

Sources & evidence

ORD record
ord-3eba801eadab42b39d76f9334974f402
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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