4-Chloro-3-nitrotoluene → HCID 13792164, compound

HRID 2294908Notes

Reaction equation

HRID 2294908 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[NH2:12][CH:13]1[CH2:18][CH2:17][N:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH2:15][CH2:14]1.C(=O)([O-])[O-].[Na+].[Na+]>[I-].[Na+].C1(O)CCCCC1>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([NH:12][CH:13]2[CH2:14][CH2:15][N:16]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH2:17][CH2:18]2)=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

Participants

6

Reactant 3

HCID 69764-Chloro-3-nitrotolueneHCID 10340Sodium CarbonateHCID 100867Ethyl 4-amino-1-piperidinecarboxylate

Product 1

HCID 13792164HCID 13792164, compoundYield 43.1%

Reagents, catalysts & solvents 2

HCID 5238Sodium IodideCatalystHCID 7966CyclohexanolSolvent2×

Conditions

Temperature
150 °C

Procedure

A mixture of 69 g of 4-chloro-3-nitro-toluene, 50 g of ethyl 4-amino-1-piperidinecarboxylate, 24 g of sodium carbonate, 0.1 g of sodium iodide and 120 mL of cyclohexanol was heated to 150° C. for 72 h. After cooling the cyclohexanol was distilled off under reduced pressure and the residue partitioned between 1 L of ethyl acetate and 1 L of water. The organic extract was dried over MgSO4 and concentrated under reduced pressure. Chromatography over silica gel, eluting with 20% ethyl acetate in cyclohexane gave 38.5 g (42.3%) of ethyl 4-(4-methyl-2-nitroanilino)-1-piperidinecarboxylate as an orange crystalline solid. 1H NMR (400 MHz, CDCl3) 8.0 (s, 1H), 7.27 (t, J=9 Hz, 1H), 6.8 (d, J=9 Hz, 1H), 4.15 (q, J=7 Hz, 2H), 4.05 (br m, 2H), 3.67 (br m, 1H), 3.10 (br t, J=11 Hz, 2H), 2.27 (s, 3H), 2.06 (br d, J=11 Hz, 2H), 1.6 (m, 2H), 1.27 (t, J=7 Hz, 4H).

Workup

  1. distillationwas distilled off under reduced pressure
  2. customthe residue partitioned between 1 L of ethyl acetate and 1 L of water
  3. extractionThe organic extract
  4. dry with materialwas dried over MgSO4
  5. concentrationconcentrated under reduced pressure
  6. washChromatography over silica gel, eluting with 20% ethyl acetate in cyclohexane

Sources & evidence

ORD record
ord-ccab13e808af4d838985cc9013dc1fa2
Source dataset
uspto-grants-1997_11
Patent number
US05691323

Reaction notes

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