Sodium Carbonate → 1-Carbethoxy-4-(5-chloro-2-nitroanilino)-piperidine

HRID 2064050Notes

Reaction equation

HRID 2064050 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:11][CH2:10][CH:9]([NH2:12])[CH2:8][CH2:7]1)=[O:5])[CH3:2].Cl[C:14]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:15]=1[N+:21]([O-:23])=[O:22].C(=O)([O-])[O-].[Na+].[Na+]>CN(C)C=O.O.C(OCC)(=O)C.[I-].[K+]>[Cl:20][C:18]1[CH:17]=[CH:16][C:15]([N+:21]([O-:23])=[O:22])=[C:14]([NH:12][CH:9]2[CH2:8][CH2:7][N:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])[CH2:11][CH2:10]2)[CH:19]=1

Participants

8

Reactant 3

HCID 10340Sodium CarbonateHCID 118992,4-DichloronitrobenzeneHCID 100867Ethyl 4-amino-1-piperidinecarboxylate

Product 1

HCID 137921661-Carbethoxy-4-(5-chloro-2-nitroanilino)-piperidineYield 65%

Reagents, catalysts & solvents 4

HCID 4875Potassium IodideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
140 °C

Procedure

Ethyl-4-amino-1-piperidine-carboxylate (29.6 g, 0.17 mol) was added to a stirred suspension of 2,4-dichloronitrobenzene (30.0 g, 0.16 mol), sodium carbonate (16.5 g, 0.16 mol) and potassium iodide (0.26 g, 0.0016 mol) in dimethylformamide (300 mL). The mixture was heated to 140° C., stirred for 15 hours and then allowed to cool. The reaction mixture was diluted with water (400 mL) and ethyl acetate (600 mL). The aqueous phase was separated and the organic phase was extracted with water (2×300 mL). The organic phase was dried over MgSO4 and evaporated under reduced pressure. The residue was purified by column chromatography on silica, eluting with ethyl acetate/hexane (1:3) to give the title compound (33.0 g, 65% yield) as an orange solid. (Rf: 0.4 (ethyl acetate/hexane 1:3))

Workup

  1. temperatureto cool
  2. customThe aqueous phase was separated
  3. extractionthe organic phase was extracted with water (2×300 mL)
  4. dry with materialThe organic phase was dried over MgSO4
  5. customevaporated under reduced pressure
  6. customThe residue was purified by column chromatography on silica
  7. washeluting with ethyl acetate/hexane (1:3)

Sources & evidence

ORD record
ord-9da7fe6bd19140d5af0eef0809b165df
Source dataset
uspto-grants-2012_10
Patent number
US08288413B2

Reaction notes

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