Sodium hydride → 4,7-bis(4-(N,N-diphenylamino)phenyl)-2-(2-methylquinolin-4-yl)-2H-benzo[d][1,2,3]triazole

HRID 1050690Notes

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.Cl[C:49]1[C:58]2[C:53](=[CH:54][CH:55]=[CH:56][CH:57]=2)[N:52]=[C:51]([CH3:59])[CH:50]=1.[H-].[Na+]>CN(C)C=O>[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:49]5[C:58]6[C:53](=[CH:54][CH:55]=[CH:56][CH:57]=6)[N:52]=[C:51]([CH3:59])[CH:50]=5)[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

Conditions

Temperature: 160 °C

Procedure

A mixture of Intermediate D (605 mg, 1.0 mmol), 4-chloroquinaldine (266 mg, 1.5 mmol), 60% NaH (60 mg, 1.5 mmol), and dimethylformamide (15 mL) was stirred under argon and heated at 160° C. for 4 days. The volatiles were removed under reduced pressure, and the residue was chromatographed using silica gel and hexane/ethyl acetate (2:1) as an eluent. The obtained product was recrystallized from ethanol to give 4,7-bis(4-(N,N-diphenylamino)phenyl)-2-(2-methylquinolin-4-yl)-2H-benzo[d][1,2,3]triazole (Example 15) as orange crystals, 520 mg (70%). 1H NMR (400 MHz, CDCl3): δ 8.73 (d, J=8.4 Hz, 1H, quinaldine), 8.13 (d, J=8.4 Hz, 1H, quinaldine), 8.07 (d, J=8.8 Hz, 4H, p-phenylene), 7.98 (s, 1H, quinaldine), 7.77 (ddd, J=8.4, 7.0 and 1.1 Hz, 1H, quinaldine), 7.73 (s, 2H, benzotriazole), 7.60 (ddd, J=8.4, 7.3 and 1.1 Hz, 1H, quinaldine), 7.25-7.30 (m, 8H, Ph), 7.21 (d, J=8.4 Hz, 4H, p-phenylene), 7.16-7.19 (m, 8H, Ph), 7.05 (tt, J=7.3 and 1.1 Hz, 4H, Ph), 2.86 (s, 3H, quinaldine). UV-vis spectrum (dichloromethane): λmax=438 nm. Fluorimetry (dichloromethane): λmax=617 nm.

Workup

customThe volatiles were removed under reduced pressure
customthe residue was chromatographed
customThe obtained product was recrystallized from ethanol

Sources & evidence

ORD record: ord-6fa3f36f40e3408882090c1d172527b2
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09382424B2

Reaction notes

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