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

HRID 2423307Notes

Reaction equation

HRID 2423307 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.CO.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

8

Reactant 4

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

Product 1

HCID 824493-Methyl-2,4-dinitroaniline

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A mixture of 2,6-dinitrotoluene (28 g, 0.15 mol) and hydroxylamine hydrochloride (28 g, 0.15 mol) was stirred in ethanol (700 mL) until completely dissolved. 2N potassium hydroxide solution in methanol (275 mL) was added all at once and the resulting mixture allowed to stir overnight at room temperature. After this time a solution of ammonium chloride (36 g) in water (175 mL) was added and the mixture stirred for an additional hour. The reaction mixture was evaporated under reduced pressure and the residue partitioned between ethyl acetate (300 mL) and saturated brine (250 mL). The ethyl acetate layer was separated, dried over magnesium sulfate and concentrated under reduced pressure. Flash chromatography of the residue (ethyl acetate/hexane (2:1)) afforded the desired product. 1H NMR (400 MHz) (CDCl3) δ 7.98 (d, J=9.4 Hz, 1H); 6.73 (d, J=9.4 Hz, 1H); 5.50 (bs, 2H); 2.59 (s, 3H).

Workup

  1. dissolutionuntil completely dissolved
  2. stirringthe mixture stirred for an additional hour
  3. customThe reaction mixture was evaporated under reduced pressure
  4. customthe residue partitioned between ethyl acetate (300 mL) and saturated brine (250 mL)
  5. customThe ethyl acetate layer was separated
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-4ea21c0133e349c6ac5dd86308903f02
Source dataset
uspto-grants-2011_06
Patent number
US07960567B2

Reaction notes

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