1-Chloro-2,4-Dinitrobenzene → HCID 59799760, compound

HRID 2074461Notes

Reaction equation

HRID 2074461 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].[CH3:14][N:15]1[CH2:20][CH2:19][CH:18]([NH2:21])[CH2:17][CH2:16]1>CCO>[N+:11]([C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[NH:21][CH:18]1[CH2:19][CH2:20][N:15]([CH3:14])[CH2:16][CH2:17]1)([O-:13])=[O:12]

Participants

4

Reactant 2

HCID 61-Chloro-2,4-DinitrobenzeneHCID 27375314-Amino-1-methylpiperidine

Product 1

HCID 59799760HCID 59799760, compoundYield 54.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
40 °C

Procedure

Chloro-2,4-dinitrobenzene 1 (2.0 g, 9.874 mmol) was dissolved in anhydrous EtOH (40 mL) in a small argon purged flask and warmed in an oil bath to 40° C. Addition of 1-Methyl-piperidin-4-ylamine 50 (1.24 g, 10.862 mmol) occurred dropwise. The solution was heated to reflux in an oil bath for 48 hours. After cooling to room temperature the solvent was removed under reduced pressure and the resulting residue partitioned between H2O and ethyl acetate and IM ammonium hydroxide solution added to adjust pH to 9. The mixture was transferred to a separatory funnel and the organic layer collected. The aqueous layer was further extracted with ethyl acetate and the combined organic layers were washed with H2O, brine (twice), dried over magnesium sulphate, filtered and then concentrated. Recrystallization of the crude solid from EtOH yielded a yellow solid 51 (2,4-Dinitro-phenyl)-(1-methyl-piperidin-4-yl)-amine Yield: 1.50 grams (54.2%). 1H NMR (DMSO) δ: 1.59-1.75 (m, 2H), 1.86-1.98 (m, 2H), 2.06-2.17 (m, 2H), 2.18 (s, 3H), 2.62-2.77 (m, 2H), 3.71-3.84 (m, 1H), 7.31 (d, 1H, J=9.7), 8.24 (dd, 1H, J=9.7, 2.7), 8.45 (d, 1H, J=7.7), 8.85 (d, 1H, J=2.6); MS (ESI): 281 (MH+, 100%).

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux in an oil bath for 48 hours
  3. temperatureAfter cooling to room temperature the solvent
  4. customwas removed under reduced pressure
  5. customthe resulting residue partitioned between H2O and ethyl acetate and IM ammonium hydroxide solution
  6. additionadded
  7. customThe mixture was transferred to a separatory funnel
  8. customthe organic layer collected
  9. extractionThe aqueous layer was further extracted with ethyl acetate
  10. washthe combined organic layers were washed with H2O, brine (twice),
  11. dry with materialdried over magnesium sulphate
  12. filtrationfiltered
  13. concentrationconcentrated
  14. customRecrystallization of the crude solid from EtOH

Sources & evidence

ORD record
ord-7d8ce501d1eb42d5b865671bd07bbfd9
Source dataset
uspto-grants-2011_04
Patent number
US07919510B2

Reaction notes

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