Dimethyl Sulfoxide → 2-Amino-4-methyl-3,5-dinitrobenzonitrile

HRID 916286Notes

Reaction equation

HRID 916286 reaction equation
[CH3:1][C:2]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:13]([O-:15])=[O:14].[NH2:16]N1C=NN=C1.CS(C)=O.CC(C)([O-])C.[Li+]>C(O)(=O)C>[NH2:16][C:8]1[C:9]([N+:10]([O-:12])=[O:11])=[C:2]([CH3:1])[C:3]([N+:13]([O-:15])=[O:14])=[CH:4][C:5]=1[C:6]#[N:7]

Participants

6

Reactant 4

HCID 679Dimethyl Sulfoxide2×HCID 114324-Amino-1,2,4-triazoleHCID 51343164-Methyl-3,5-dinitrobenzonitrileHCID 236647642-Propanol, 2-methyl-, lithium salt (1:1)

Product 1

HCID 167267892-Amino-4-methyl-3,5-dinitrobenzonitrile

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
22.5 °C

Procedure

A solution of 4-methyl-3,5-dinitrobenzonitrile (10.5 kg; preparation see U.S. Pat. No. 3,162,675), 4-amino-4H-1,2,4-triazole (17.0 kg) and dimethyl sulfoxide (68.6 kg) was dosed into a mixture of lithium tert-butoxide (12.2 kg) and dimethyl sulfoxide (106.6 kg) over about 50 min, while maintaining the temperature of each solution at 20-25° C. After aging at 20-25° C. for about 2 h, acetic acid (8.9 kg) was dosed into the reaction mixture at about 20° C. over about 10 min. The product was crystallized by dosing water (158 L) into the reaction mixture over about 1.5 h at about 20° C. The product slurry was cooled to 10-15° C. and held at this temperature for about 45 min. The resultant slurry was filtered, and washed with water (106 L). The wet cake obtained was dried in a vacuum tray dryer at about 50° C. and 30 Torr to provide 2-amino-4-methyl-3,5-dinitrobenzonitrile as an orange-brown solid.

Workup

  1. custompreparation
  2. customThe product was crystallized
  3. customover about 1.5 h
  4. customat about 20° C
  5. temperatureThe product slurry was cooled to 10-15° C.
  6. waitheld at this temperature for about 45 min
  7. filtrationThe resultant slurry was filtered
  8. washwashed with water (106 L)
  9. customThe wet cake obtained
  10. customwas dried in a vacuum tray dryer at about 50° C.

Sources & evidence

ORD record
ord-f81f1ace4ad44ce2b43f29a998567d05
Source dataset
uspto-grants-2007_09
Patent number
US07268255B2

Reaction notes

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