4-(3,4-Dinitrobenzyl)morpholine → 4-Morpholin-4-yl methyl-benzene-1,2-diamine

HRID 1639642Notes

Reaction equation

HRID 1639642 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:14]=[CH:15][C:16]=1[N+:17]([O-])=O)[CH2:7][N:8]1[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1)([O-])=O>C(O)C>[N:8]1([C:7]2[C:15]([CH3:14])=[C:16]([NH2:17])[C:4]([NH2:1])=[CH:5][CH:6]=2)[CH2:9][CH2:10][O:11][CH2:12][CH2:13]1

Participants

3

Reactant 1

HCID 251933104-(3,4-Dinitrobenzyl)morpholine

Product 1

HCID 667217534-Morpholin-4-yl methyl-benzene-1,2-diamineYield 98.6%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
20 °C

Procedure

4-(3,4-Dinitro-benzyl)-morpholine (0.800 Kg, 2.99 mol, 1.0 wt), and ethanol (11.20 L, 14.0 vol) were charged to a suitable flask and stirred at 15 to 25° C. and a vacuum/nitrogen purge cycle was performed three times. 10% Palladium on carbon (10% Pd/C, 50% wet paste, 0.040 Kg, 0.05 wt wet weight) was slurried in ethanol (0.80 L, 1.0 vol) and added to the reaction. The mixture was cooled to 10 to 20° C. and a vacuum/nitrogen purge cycle was performed three times. A vacuum/hydrogen purge cycle was performed three times and the reaction was stirred under a hydrogen atmosphere at 10 to 20° C. Reaction completion was determined by 1H NMR analysis (d6-DMSO), typically 14 to 20 hours. A vacuum/nitrogen purge cycle was performed three times and the reaction mixture was filtered through glass microfibre paper under nitrogen. The filter-cake was washed with ethanol (3×0.80 L, 3×1.0 vol) and the combined filtrate and washes were concentrated to dryness under vacuum at 35 to 45° C. to give 4-morpholin-4-yl-methyl-benzene-1,2-diamine (0.611 Kg 98.6%) as a brown solid.

Workup

  1. customa vacuum/nitrogen purge cycle
  2. additionadded to the reaction
  3. temperatureThe mixture was cooled to 10 to 20° C.
  4. customa vacuum/nitrogen purge cycle
  5. customA vacuum/hydrogen purge cycle
  6. stirringthe reaction was stirred under a hydrogen atmosphere at 10 to 20° C
  7. customReaction completion
  8. customwas determined by 1H NMR analysis (d6-DMSO), typically 14 to 20 hours
  9. customA vacuum/nitrogen purge cycle
  10. filtrationthe reaction mixture was filtered through glass microfibre paper under nitrogen
  11. washThe filter-cake was washed with ethanol (3×0.80 L, 3×1.0 vol)
  12. concentrationthe combined filtrate and washes were concentrated to dryness under vacuum at 35 to 45° C.

Sources & evidence

ORD record
ord-b3d82893748e48b49013d889a238f3e9
Source dataset
uspto-grants-2012_02
Patent number
US08110573B2

Reaction notes

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