4-Methyl-3-nitroaniline → N-(4-Methyl-3-nitro-phenyl)-4-(4-methyl-piperazin-1-ylmethyl)-benzamide

HRID 1160120Notes

Reaction equation

HRID 1160120 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:8]=[CH:9][C:10]=1[CH3:11])[NH2:7])([O-:3])=[O:2].C([Al](CC(C)C)CC(C)C)C(C)C.C[O:26][C:27](=O)[C:28]1[CH:33]=[CH:32][C:31]([CH2:34][N:35]2[CH2:40][CH2:39][N:38]([CH3:41])[CH2:37][CH2:36]2)=[CH:30][CH:29]=1>C1(C)C=CC=CC=1>[CH3:11][C:10]1[CH:9]=[CH:8][C:6]([NH:7][C:27](=[O:26])[C:28]2[CH:29]=[CH:30][C:31]([CH2:34][N:35]3[CH2:36][CH2:37][N:38]([CH3:41])[CH2:39][CH2:40]3)=[CH:32][CH:33]=2)=[CH:5][C:4]=1[N+:1]([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 83904-Methyl-3-nitroanilineHCID 782222Methyl 4-((4-methylpiperazin-1-yl)methyl)benzoateHCID 16682931Triisobutylaluminum3×

Product 1

HCID 29984087N-(4-Methyl-3-nitro-phenyl)-4-(4-methyl-piperazin-1-ylmethyl)-benzamide

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To a solution of 10.95 g (72 mmol) of 3-nitro-4-methyl-aniline in 80 ml of toluene is added a solution of triisobutylaluminium (28% in hexane), 66.5 ml (61 mmol) over a period of 30 min at 0° C. followed by the addition of a solution of 4-(4-methyl-piperazin-1-ylmethyl)-benzoic acid methyl ester (14.9 g, 60 mmol) in toluene (30 ml) during 1 hour at 0° C. under an atmosphere of argon. After stirring for 12 h at room temperature an other portion of triisobutylaluminium (66.5 ml (61 mmol) is added to the dark brown reaction mixture. The mixture is stirred for additional 6 h, then 2 additional small portions of triisobutylaluminium (each 18 ml, 18 mmol) are added and stirring is continued for several hours at room temperature. After acidic and basic workup with sulfuric acid and NaOH the combined organic toluene phases are evaporated in vacuo to give a brown crude product which was crystallized from t-butyl methyl ether to give the title compound as brownish yellow crystals: first crop (11.65 g), sec. crop (3.8 g) and a third crop (1.2 g). in summary 16.65 g (75.3%).

Workup

  1. additionis added to the dark brown reaction mixture
  2. stirringstirring
  3. waitis continued for several hours at room temperature
  4. customAfter acidic and basic workup with sulfuric acid and NaOH the combined organic toluene phases are evaporated in vacuo
  5. customto give a brown crude product which
  6. customwas crystallized from t-butyl methyl ether

Sources & evidence

ORD record
ord-6894cefdb06d4e07bfef1539f70e3c74
Source dataset
uspto-grants-2010_10
Patent number
US07816359B2

Reaction notes

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