Nitric Acid → 5,7-Dihydro-5,5,7,7-tetramethyl-3-(3-nitrophenyl)furo(3,4-e)-as-triazine 4-oxide

HRID 1658235Notes

Reaction equation

HRID 1658235 reaction equation
[N+:1]([O-:4])(O)=[O:2].FC(F)(F)S(O)(=O)=O.[CH3:13][C:14]1([CH3:32])[C:18]2[N+:19]([O-:29])=[C:20]([C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)[N:21]=[N:22][C:17]=2[C:16]([CH3:31])([CH3:30])[O:15]1.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[CH3:13][C:14]1([CH3:32])[C:18]2[N+:19]([O-:29])=[C:20]([C:23]3[CH:28]=[CH:27][CH:26]=[C:25]([N+:1]([O-:4])=[O:2])[CH:24]=3)[N:21]=[N:22][C:17]=2[C:16]([CH3:31])([CH3:30])[O:15]1

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 62406Trifluoromethanesulfonic acidHCID 516892Sodium BicarbonateHCID 64127205,5,7,7-tetramethyl-4-oxido-3-phenylfuro[3,4-e][1,2,4]triazin-4-ium

Product 1

HCID 727295,7-Dihydro-5,5,7,7-tetramethyl-3-(3-nitrophenyl)furo(3,4-e)-as-triazine 4-oxide

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
25 °C

Procedure

To a mixture of 0.2 ml (0.005 mole) of fuming nitric acid and 1.5 grams (0.01 mole) of trifluoromethanesulfonic acid in 15 ml. anhydrous methylene chloride, after allowing the resulting mixture to be stirred for 1 hour at 25°C., there is added dropwise maintaining the temperature at -30°C., 0.542 grams (0.002 mole) of 5,7-dihydro-5,5,7,7-tetramethyl-3-phenylfuro [3,4-e]-as-triazine-4-oxide in 15 ml. of anhydrous methylene chloride. The resulting heterogeneous mixture is stirred at 25°C. for 72 hours, poured onto ice, and neutralized with solid sodium bicarbonate. The organic layer is removed and the aqueous phase extracted several times with methylene chloride. The combined organic layers are washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate and evaporated to give a white solid. The resulting solid is recrystallized from methylene chloride/hexane to give 5,7-dihydro-5,5,7,7-tetramethyl-3-(m-nitrophenyl)-furo[3,4-e]-as-triazine-4-oxide, m.p. 202°-204°C.

Workup

  1. additionthere is added dropwise
  2. temperaturemaintaining the temperature at -30°C.
  3. stirringThe resulting heterogeneous mixture is stirred at 25°C. for 72 hours
  4. additionpoured onto ice
  5. customThe organic layer is removed
  6. extractionthe aqueous phase extracted several times with methylene chloride
  7. washThe combined organic layers are washed with saturated aqueous sodium chloride solution
  8. dry with materialdried over magnesium sulfate
  9. customevaporated
  10. customto give a white solid
  11. customThe resulting solid is recrystallized from methylene chloride/hexane

Sources & evidence

ORD record
ord-c4deb43b7169493586ed606372f41474
Source dataset
uspto-grants-1976_06
Patent number
US03963713

Reaction notes

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