5-Bromo-2-nitrobenzotrifluoride → HCID 86719493, compound

HRID 1772258Notes

Reaction equation

HRID 1772258 reaction equation
[CH3:1][CH:2]([Si:4]([CH:16]([CH3:18])[CH3:17])([CH:13]([CH3:15])[CH3:14])[O:5][C:6]1[CH:12]=[CH:11][C:9]([NH2:10])=[CH:8][CH:7]=1)[CH3:3].Br[C:20]1[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[C:22]([C:29]([F:32])([F:31])[F:30])[CH:21]=1.C(O[Na])(C)(C)C>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[N+:26]([C:23]1[CH:24]=[CH:25][C:20]([NH:10][C:9]2[CH:11]=[CH:12][C:6]([O:5][Si:4]([CH:16]([CH3:18])[CH3:17])([CH:2]([CH3:1])[CH3:3])[CH:13]([CH3:15])[CH3:14])=[CH:7][CH:8]=2)=[CH:21][C:22]=1[C:29]([F:30])([F:31])[F:32])([O-:28])=[O:27]

Participants

7

Reactant 3

HCID 1361715-Bromo-2-nitrobenzotrifluorideHCID 86719492HCID 86719492, compoundHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 86719493HCID 86719493, compoundYield 31.4%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 4-[[tris(propan-2-yl)silyl]oxy]aniline (15 g, 56 mmol) in toluene (100 ml) was added 4-bromo-1-nitro-2-(trifluoromethyl)benzene (22.84 g, 84.6 mmol, 1.5 eq.), Pd2(dba)3 (2.34 g, 2.3 mmol, 4 mol %), BINAP (710 mg, 1.1 mmol, 2 mol %) and t-BuONa (10.87 g, 113.2 mmol, 2 eq.). The mixture was stirred under nitrogen overnight at 100° C. (oil bath). The reaction mixture was concentrated under vacuum to give a residue, which was purified by silica gel column chromatography using 10% ethyl acetate in petroleum ether to afford 4-nitro-3-(trifluoromethyl)-N-(4-[[tris(propan-2-yl)silyl]oxy]phenyl)aniline as a orange solid (8 g, 31%); (ES, m/z): [M+H]+ 455; 1H NMR (300 MHz, CDCl3): δ 7.97 (d, J=6.0 Hz, 1H), 7.05-7.09 (m, 3H), 6.87-6.96 (m, 3H), 6.18 (s, 1H), 1.26-1.33 (m, 3H), 1.13 (s, 18H).

Workup

  1. concentrationThe reaction mixture was concentrated under vacuum
  2. customto give a residue, which
  3. customwas purified by silica gel column chromatography

Sources & evidence

ORD record
ord-c7f5a66efb8344b0b0031db72008ad70
Source dataset
uspto-grants-2016_02
Patent number
US09249102B2

Reaction notes

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