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

HRID 1047550Notes

Reaction equation

HRID 1047550 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>CN(C=O)C.C1COCC1>[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

7

Reactant 4

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

Product 1

HCID 13043973(3,4-Dinitrophenyl)(morpholino)methanoneYield 56.6%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 3,4-dinitrobenzoic acid (200 mg, 0.943 mmol) and DMF (2 drops) in THF (7 mL) was treated with thionyl chloride (0.14 mL, 224 mmol) and then heated at reflux for 2.5 h. The mixture was cooled to 0° C. and triethylamine (286 mg, 1.883 mmol) was added over 25 min while keeping the internal temperature at 0° C. Morpholine (164 mg, 1.883 mmol) was added. The mixture was stirred overnight and allowed to warm to ambient temperature. Purification by flash chromatography afforded the title compound (150 mg). 1H NMR (400 MHz, CD3OD): δ 8.36 (s, 1H), 8.10 (d, 1H, J=8.8 Hz), 7.28 (d, 1H, J=9.2 Hz), 3.79 (m, 4H), 3.16 (m, 4H).

Workup

  1. temperatureheated
  2. temperatureat reflux for 2.5 h
  3. customat 0° C
  4. temperatureto warm to ambient temperature
  5. customPurification by flash chromatography

Sources & evidence

ORD record
ord-7d6739403c8740dca5da36cf7d61bf52
Source dataset
uspto-grants-2013_10
Patent number
US08569511B2

Reaction notes

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