1,4-Dibromobenzene → 4-(4-Bromophenyl)morpholin-3-one

HRID 1408960Notes

Reaction equation

HRID 1408960 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1.[NH:9]1[CH2:14][CH2:13][O:12][CH2:11][C:10]1=[O:15].P([O-])([O-])([O-])=O.[K+].[K+].[K+].CNCCNC>O1CCOCC1.[Cu]I>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([N:9]2[CH2:14][CH2:13][O:12][CH2:11][C:10]2=[O:15])=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 78041,4-DibromobenzeneHCID 8070N,N'-DimethylethylenediamineHCID 62657Potassium Phosphate, TribasicHCID 669533-Morpholinone

Product 1

HCID 179827074-(4-Bromophenyl)morpholin-3-oneYield 67.6%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
105 °C

Procedure

A solution of 1,4-dibromobenzene (283 mg, 1.200 mmol), morpholin-3-one (101.104 mg, 1.000 mmol), dibasic potassium phosphate (348 mg, 2.000 mmol), copper (I) iodide (38.1 mg, 0.200 mmol) and N,N′-dimethylethylenediamine (0.043 ml, 0.400 mmol) in dioxane (3 ml) was purged with nitrogen for 2 min, sealed in a reaction vial and heated in a heating block at 105° C. for 15 h. The crude product mixture was filtered, and charged to a 12 g silica gel cartridge which was eluted with 0-50% EtOAc in hexanes to give the title compound (173 mg, 0.676 mmol, 67.6% yield) as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 10.56 (1H, none), 7.55 (2 H, d, J=8.80 Hz), 7.24 (2 H, d, J=8.58 Hz), 4.04 (2 H, dd, J=5.83, 4.29 Hz), 3.73-3.79 (2 H, m). HPLC (condition F): ret. Time 2.213 min; LC/MS [m/z, (M+H)] 258.0.

Workup

  1. customsealed in a reaction vial
  2. filtrationThe crude product mixture was filtered
  3. additioncharged to a 12 g silica gel cartridge which
  4. washwas eluted with 0-50% EtOAc in hexanes

Sources & evidence

ORD record
ord-514853be68fc4b3e9ce57fda99c9802c
Source dataset
uspto-grants-2014_12
Patent number
US08921368B2

Reaction notes

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