Dimethylformamide → 6-(4,7-bis(4-(N,N-diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)-2-hexyl-1H-benzo[de]isoquinoline-1,3(2H)-dione

HRID 1050693Notes

Reaction equation

HRID 1050693 reaction equation
[C:1]1([N:7]([C:14]2[CH:19]=[CH:18][C:17]([C:20]3[C:28]4[C:24](=[N:25][NH:26][N:27]=4)[C:23]([C:29]4[CH:34]=[CH:33][C:32]([N:35]([C:42]5[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=5)[C:36]5[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=5)=[CH:31][CH:30]=4)=[CH:22][CH:21]=3)=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:49]1[CH:50]=[CH:51][C:52]2[C:53](=[O:69])[N:54]([CH2:63][CH2:64][CH2:65][CH2:66][CH2:67][CH3:68])[C:55](=[O:62])[C:56]3[C:61]=2[C:60]=1[CH:59]=[CH:58][CH:57]=3.C(=O)([O-])[O-].[K+].[K+].CN(C)C=O>C(OCC)(=O)C.[Cu]I>[C:8]1([N:7]([C:14]2[CH:15]=[CH:16][C:17]([C:20]3[C:28]4[C:24](=[N:25][N:26]([C:59]5[CH:58]=[CH:57][C:56]6[C:55](=[O:62])[N:54]([CH2:63][CH2:64][CH2:65][CH2:66][CH2:67][CH3:68])[C:53](=[O:69])[C:52]7[C:61]=6[C:60]=5[CH:49]=[CH:50][CH:51]=7)[N:27]=4)[C:23]([C:29]4[CH:34]=[CH:33][C:32]([N:35]([C:36]5[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=5)[C:42]5[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=5)=[CH:31][CH:30]=4)=[CH:22][CH:21]=3)=[CH:18][CH:19]=2)[C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 17929730HCID 17929730, compoundHCID 866799124,7-bis(4-(N,N-diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799156-(4,7-bis(4-(N,N-diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)-2-hexyl-1H-benzo[de]isoquinoline-1,3(2H)-dione

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
160 °C

Procedure

A mixture of Intermediate D (1.00 g, 1.65 mmol), 6-bromo-2-hexyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (720 mg, 2.0 mmol), potassium carbonate (276 mg, 2.0 mmol), CuI (382 mg, 2.0 mmol), and dimethylformamide (12 mL) was stirred under argon and heated at 160° C. for 3 days. After cooling, the reaction mixture was diluted with ethyl acetate (100 mL), washed with water (3×50 mL), dried over magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica gel, hexane/dichloromethane 1:1) and washing with ethanol to give 6-(4,7-bis(4-(N,N-diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)-2-hexyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (Example 18), brown-violet crystals, 445 mg (30%). 1H NMR (400 MHz, CDCl3): δ 9.08 (dd, J=8.4 and 1.1 Hz, 1H, naphthalene), 8.74 (d, J=7.6 Hz, 1H, naphthalene), 7.69 (dd, J=7.3 and 1.1 Hz, 1H, naphthalene), 8.43 (d, J=8.1 Hz, 1H, naphthalene), 8.07 (d, J=8.8 Hz, 4H, p-phenylene), 7.85 (dd, J=8.4 and 7.3 Hz, 1H, naphthalene), 7.74 (s, 2H, benzotriazole), 7.28 (m, 8H, Ph), 7.21 (d, J=8.4 Hz, 4H, p-phenylene), 7.18 (m, 8H, Ph), 7.05 (tt, J=7.3 and 1.1 Hz, 4H, Ph). UV-vis spectrum (dichloromethane): λmax=381 nm. Fluorimetry (dichloromethane): λmax=481 nm.

Workup

  1. temperatureAfter cooling
  2. washwashed with water (3×50 mL)
  3. dry with materialdried over magnesium sulfate
  4. customthe solvent was removed under reduced pressure
  5. customThe crude product was purified by column chromatography (silica gel, hexane/dichloromethane 1:1)
  6. washwashing with ethanol

Sources & evidence

ORD record
ord-8c20ba8143ee4a97a2c6bd24c7011ff6
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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