Morpholine → 4-(2-Fluoro-4-nitrophenyl)morpholine

HRID 1471000Notes

Reaction equation

HRID 1471000 reaction equation
[NH:1]1[CH2:6][CH2:5][O:4][CH2:3][CH2:2]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[F:15][C:16]1[CH:17]=[C:18]([N+:23]([O-:25])=[O:24])[CH:19]=[CH:20][C:21]=1F>CS(C)=O.C(OCC)(=O)C>[F:15][C:16]1[CH:17]=[C:18]([N+:23]([O-:25])=[O:24])[CH:19]=[CH:20][C:21]=1[N:1]1[CH2:6][CH2:5][O:4][CH2:3][CH2:2]1

Participants

6

Reactant 3

HCID 8083MorpholineHCID 62657Potassium Phosphate, TribasicHCID 1230531,2-Difluoro-4-nitrobenzene

Product 1

HCID 29054894-(2-Fluoro-4-nitrophenyl)morpholineYield 103.1%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

A suspension of morpholine (4.72 mL, 4.72 g, 54.2 mmol) and dibasic potassium phosphate (9.44 g, 54.2 mmol) in DMSO (27 mL) was treated with 3,4-difluoronitrobenzene (3.0 mL, 4.31 g, 27.1 mmol) was warmed at 60° C. for 18 h. The solution was cooled and diluted with ethyl acetate and extracted with water (3×) and saturated sodium chloride solution. Drying (Na2SO4) and concentration in vacuo afforded the title compound (6.32 g, ca. 100%) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ 8.00 (ddd, J=9.0, 2.6, 0.9 Hz, 1H), 7.92 (dd, J=13.1, 2.6 Hz, 1H), 6.92 (t, J=8.8 Hz, 1H), 3.88 (m, 4H), 3.29 (dd, J=5.5, 4.0 Hz, 4H). MS+DCI m/z (rel abundance) 227 (10, M+H), 244 (100, M+NH4).

Workup

  1. temperatureThe solution was cooled
  2. extractionextracted with water (3×) and saturated sodium chloride solution
  3. customDrying
  4. concentration(Na2SO4) and concentration in vacuo

Sources & evidence

ORD record
ord-acf8e193bb944bedaca080c8a27739a2
Source dataset
uspto-grants-2015_04
Patent number
US09006387B2

Reaction notes

Loading…