Morpholine → (3,4-Dinitrophenyl)(morpholino)methanone

HRID 1639629Notes

Reaction equation

HRID 1639629 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:10]=[CH:11][C:12]=1[N+:13]([O-:15])=[O:14])[C:7]([OH:9])=O)([O-:3])=[O:2].S(Cl)(Cl)=O.C(N(CC)CC)C.[NH:27]1[CH2:32][CH2:31][O:30][CH2:29][CH2:28]1>C1COCC1.O.CN(C=O)C>[N+:1]([C:4]1[CH:5]=[C:6]([C:7]([N:27]2[CH2:32][CH2:31][O:30][CH2:29][CH2:28]2)=[O:9])[CH:10]=[CH:11][C:12]=1[N+:13]([O-:15])=[O:14])([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 8083Morpholine2×HCID 8471TriethylamineHCID 107093,4-Dinitrobenzoic acidHCID 24386Thionyl Chloride

Product 1

HCID 13043973(3,4-Dinitrophenyl)(morpholino)methanoneYield 96.1%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 3,4-dinitrobenzoic acid (10 g, 47 mmol, 1 eq.) and DMF (0.1 mL) in THF (100 mL) was treated with thionyl chloride (4.5 mL, 62 mmol, 1.3 eq.) then heated to reflux for 2.5 h. The mixture was cooled in ice then triethylamine (10 mL, 71 mmol, 1.1 eq.) was added over 20 min, keeping internal temperature<5° C. Morpholine (6.2 mL, 71 mmol, 1.5 eq) was added to the resulting thick yellow suspension over 15 min, keeping internal temperature<10° C. The ice-bath was removed and the mixture allowed to warm to r.t. After 15 min, a further portion of morpholine (1 mL, 11 mmol, 0.24 eq.) was added and the mixture stirred overnight. The mixture was diluted with water (250 mL) and cooled in ice. A beige solid was filtered off under suction, washed with a further portion of cold water (25 mL) and dried in vacuo to afford the title compound (12.7 g, 96%).

Workup

  1. temperaturethen heated
  2. temperatureto reflux for 2.5 h
  3. temperatureThe mixture was cooled in ice
  4. customtemperature<5° C
  5. customtemperature<10° C
  6. customThe ice-bath was removed
  7. temperaturecooled in ice
  8. filtrationA beige solid was filtered off under suction
  9. washwashed with a further portion of cold water (25 mL)
  10. customdried in vacuo

Sources & evidence

ORD record
ord-880b650c2bdd44bb9475f5111fd93103
Source dataset
uspto-grants-2012_02
Patent number
US08110573B2

Reaction notes

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