Cesium carbonate → 2,2'-Oxybis(nitrobenzene)

HRID 1017049Notes

Reaction equation

HRID 1017049 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[C:11](=[O:14])([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.C(OCC)(=O)C>[N+:8]([C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[O:14][C:11]1[CH:5]=[CH:6][CH:7]=[CH:2][C:3]=1[N+:8]([O-:10])=[O:9])([O-:10])=[O:9]

Participants

5

Reactant 2

HCID 10796Cesium carbonateHCID 113411-Bromo-2-nitrobenzene

Product 1

HCID 18096712,2'-Oxybis(nitrobenzene)Yield 41.7%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3-[[[3[(1,1,2,2-tetrafluoroethoxy)phenyl]methyl](3,3,3-trifluoro-2-hydroxypropyl)amino]phenol (100 mg, 0.23 mmol), 1-bromo-2-nitrobenzene (52.4 mg, 0.26 mmol), copper(I) trifluoromethanesulfonate benzene complex (3 mg, 2.5 mol %) and cesium carbonate (100 mg, 0.31 mmol) in toluene (1 mL) and ethyl acetate (1 mL) was heated at 95° C. in a sealed vial for 4 d. The reaction mixture was filtered through celite, and the solvent was evaporated. The residue was purified by reverse phase HPLC eluting with 50% to 90% acetonitrile in water to afford 14.1 mg (11%) of the desired 2-nitrophenyl ether product as an orange oil. HRMS calcd. for C24H20F7N2O5: 549.1260 [M+H]+, found: 549.1235. 1H NMR (CDCl3) δ3.63 (dd, 1H), 3.84 (dd, 1H), 4.35-4.42 (m, 1), 4.64 (s, 2H), 5.90 (tt, 1H), 6.47-6.67 (m, 3H), 6.98-7.50 (m, 8H), 7.97 (d, 1H).

Workup

  1. filtrationThe reaction mixture was filtered through celite
  2. customthe solvent was evaporated
  3. customThe residue was purified by reverse phase HPLC
  4. washeluting with 50% to 90% acetonitrile in water

Sources & evidence

ORD record
ord-c888e14fd0a544ed9fe9b534e40f5160
Source dataset
uspto-grants-2002_11
Patent number
US06476075B1

Reaction notes

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