Triethylamine → N-[4-(4-bromophenoxy)benzyl]-N-(2,4-difluorobenzyl)-2-methyl-3-nitroaniline

HRID 1370816Notes

Reaction equation

HRID 1370816 reaction equation
[F:1][C:2]1[CH:27]=[C:26]([F:28])[CH:25]=[CH:24][C:3]=1[CH2:4][N:5]([CH2:16][C:17]1[CH:22]=[CH:21][C:20]([OH:23])=[CH:19][CH:18]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[C:8]([N+:12]([O-:14])=[O:13])[C:7]=1[CH3:15].[Br:29][C:30]1[CH:35]=[CH:34][C:33](B(O)O)=[CH:32][CH:31]=1.C(N(CC)CC)C>C(Cl)Cl.CC([O-])=O.CC([O-])=O.[Cu+2]>[Br:29][C:30]1[CH:35]=[CH:34][C:33]([O:23][C:20]2[CH:21]=[CH:22][C:17]([CH2:16][N:5]([CH2:4][C:3]3[CH:24]=[CH:25][C:26]([F:28])=[CH:27][C:2]=3[F:1])[C:6]3[CH:11]=[CH:10][CH:9]=[C:8]([N+:12]([O-:14])=[O:13])[C:7]=3[CH3:15])=[CH:18][CH:19]=2)=[CH:32][CH:31]=1

Participants

6

Reactant 3

HCID 8471Triethylamine2×HCID 79599(4-Bromophenyl)boronic acid2×HCID 18512160N-(2,4-difluorobenzyl)-N-(4-hydroxybenzyl)-2-methyl-3-nitroaniline

Product 1

HCID 18511981N-[4-(4-bromophenoxy)benzyl]-N-(2,4-difluorobenzyl)-2-methyl-3-nitroanilineYield 62%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalyst2×HCID 6344DichloromethaneSolvent

Procedure

The product from Example 33A (1.0 g, 2.6 mmoles), 4 Å molecular sieves, Cu(OAc)2 (0.71 g, 3.91 mmoles) and 4-bromophenylboronic acid (1.57 g, 7.81 mmoles) in CH2Cl2 (20 mL) was treated with triethylamine (1.81 mL, 13.0 mmoles) and the resulting solution was stirred vigorously overnight. An additional equivalent of Cu(OAc)2, 4-bromophenylboronic acid, and triethylamine were added and the reaction mixture was stirred vigorously for 5 hours. The mixture was filtered through a 1 inch pad of Celite using CH2Cl2 and the filtrate was concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, 10:1 hexanes:ethyl acetate) to provide the title compound as a yellow oil (0.87 g, 62%).

Workup

  1. stirringthe reaction mixture was stirred vigorously for 5 hours
  2. filtrationThe mixture was filtered through a 1 inch pad of Celite
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. customThe residue was purified by flash chromatography (silica gel, 10:1 hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-1fd96aef9b5c4e1591ece1e371e5bce4
Source dataset
uspto-grants-2003_06
Patent number
US06583180B2

Reaction notes

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