2,6-Dinitrotoluene → 3-Methyl-2,4-dinitroaniline

HRID 618212Notes

Reaction equation

HRID 618212 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[C:5]=1[CH3:13])([O-:3])=[O:2].Cl.[NH2:15]O.[OH-].[K+].[Cl-].[NH4+]>C(O)C.O>[N+:1]([C:4]1[C:5]([CH3:13])=[C:6]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:8][C:9]=1[NH2:15])([O-:3])=[O:2]

Participants

7

Reactant 4

HCID 118132,6-DinitrotolueneHCID 14797Potassium HydroxideHCID 25517Ammonium ChlorideHCID 443297Hydroxyamine hydrochloride

Product 1

HCID 824493-Methyl-2,4-dinitroaniline

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

2,4-dinitro-3-methylaniline was prepared by a modification of the procedure described by Meisenheimer, et al., Chem. Ber. (1906) 39:2533. A mixture of 2,6-dinitrotoluene (55.0 g) and hydroxylamine hydrochloride (55.0 g) was stirred in 1.4 L of ethanol until solution took place. 2N Potassium hydroxide solution (550 mL) was added all at once and the resulting mixture allowed to stir for 24 hr. A solution of ammonium chloride (71 g) in water (350 mL) was added and the mixture stirred for an additional hour. The reaction mixture was evaporated under reduced pressure. The residue was partioned between ethyl acetate (750 mL) and 50% saturated sodium chloride solution (500 mL). The ethyl acetate extract was separated and dried over magnesium sulfate. Evaporation under reduced pressure afforded a crude product (52.6 g) which was flash chromatographed on silica and eluted, first with ethyl acetate:hexane (1:3), then with ethyl acetate:hexane (1:2) to afford 36.0 g of product, mp 126.7-131.4° C.

Workup

  1. stirringthe mixture stirred for an additional hour
  2. customThe reaction mixture was evaporated under reduced pressure
  3. extractionThe ethyl acetate extract
  4. customwas separated
  5. dry with materialdried over magnesium sulfate
  6. customEvaporation under reduced pressure
  7. customafforded a crude product (52.6 g) which

Sources & evidence

ORD record
ord-2bb29aa8295d4acca9c9c06989899678
Source dataset
uspto-grants-1999_09
Patent number
US05952362

Reaction notes

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