2,4,6-Trinitrotoluene → 4-Hydroxylamino-2,6-dinitrotoluene

HRID 17772

Reaction equation

HRID 17772 reaction equation
[CH3:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][C:5]([N+:11]([O-])=[O:12])=[CH:4][C:3]=1[N+:14]([O-:16])=[O:15].C1C=C2C(C(O)(O)C(=O)C2=CC=1)=O.[OH-].[Na+]>C(OCC)(=O)C.Cl>[CH3:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][C:5]([NH:11][OH:12])=[CH:4][C:3]=1[N+:14]([O-:16])=[O:15]

Participants

6

Reactant 3

HCID 83762,4,6-TrinitrotolueneHCID 10236NinhydrinHCID 14798Sodium Hydroxide

Product 1

HCID 53754694-Hydroxylamino-2,6-dinitrotolueneYield 38.1%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of TNT (1.4 g, 6.16 mmol) in ethyl acetate (20 ml) was added a solution/suspension of stannous chloride (4.2 g, 22.22 mmol) in HCl (7.5 ml). An immediate yellow colour resulted. Stirring was continued until TLC (A) and ninhydrin development indicated the conversion of starting materials. The acidic solution was made basic by addition of NaOH solution (1M) and then extracted with saturated potassium chloride solution (4×10 ml). The organic layer was dried over sodiumsulphate and purified by column chromatography, eluting with dichloromethane to afford [7] as a yellow/orange solid (500 mg, 38%). Crystallisation from-chloroform afforded [7] as fine orange needles (220 mg). Rf (B) 0.18; δH(400 MHz; Acetone-d6) 2.29 (3H, s, CH3) 8.04 (1H, s, Ar—H) 8.19 (1H, s, Ar—H) 8.39 (1H, s, NOH) 8.42 (1H, s, NOH); m/z (EI−LR) 213 [(M) calc. for C7H7N3O5 213]; (Found C, 38.02; H, 2.07; N, 18.84. C7H7N3O5 requires C, 39.43; H, 3.28; N, 19.72%).

Workup

  1. customAn immediate yellow colour resulted
  2. extractionextracted with saturated potassium chloride solution (4×10 ml)
  3. dry with materialThe organic layer was dried over sodiumsulphate
  4. custompurified by column chromatography
  5. washeluting with dichloromethane

Sources & evidence

ORD record
ord-93c95c13ff9043a596b858197e3d206d
Source dataset
uspto-grants-2010_06
Patent number
US07741102B2

Linked notes

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