Water → 8-acetyl-7,8-dihydro-6,6-dimethyl-6H-[1,2,5]oxadiazolo[3,4-g][1,4]benzoxazine 3-oxide

HRID 1197774Notes

Reaction equation

HRID 1197774 reaction equation
[C:1]([N:4]1[C:9]2[CH:10]=[C:11]([NH2:17])[C:12]([N+:14]([O-:16])=[O:15])=[CH:13][C:8]=2[O:7][C:6]([CH3:19])([CH3:18])[CH2:5]1)(=[O:3])[CH3:2].N([O-])=O.[Na+].[N-]=[N+]=[N-].[Na+].O>Cl>[C:1]([N:4]1[C:9]2=[CH:10][C:11]3[C:12](=[N+:14]([O-:16])[O:15][N:17]=3)[CH:13]=[C:8]2[O:7][C:6]([CH3:19])([CH3:18])[CH2:5]1)(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 962WaterHCID 33557Sodium AzideHCID 191048204-acetyl 6-amino-3,4-dihydro-2,2-dimethyl-7-nitro-2H-1,4-benzoxazineHCID 23668193Sodium Nitrite2×

Product 1

HCID 191048148-acetyl-7,8-dihydro-6,6-dimethyl-6H-[1,2,5]oxadiazolo[3,4-g][1,4]benzoxazine 3-oxideYield 50.8%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

To a suspension of 530 mg 4-acetyl 6-amino-3,4-dihydro-2,2-dimethyl-7-nitro-2H-1,4-benzoxazine in 3 ml 5N HCl, was added dropwise 3 ml aqueous solution containing 156 mg sodium nitrite under ice cooling, the mixture was stirred for one hour under ice cooling, 1 ml aqueous solution containing 73 mg sodium nitrite was further added dropwise, and the resulting mixture was stirred for ten minutes. To the reaction mixture thus obtained, was added dropwise 3 ml aqueous solution containing 137 mg sodium azide under ice cooling, and the mixture was stirred for 90 minutes. After addition of 10 ml water, the precipitate which separated out was collected by filtration, and its solution in 5 ml toluene was heated under reflux for eight hours. The reaction mixture was diluted with ethyl acetate, the diluted solution was dried over anhydrous magnesium sulfate, and the solvents were distilled off from the dried solution. The residue was subjected to column chromatography on silica gel, the crystals obtained by elution with a 50:1 mixture of chloroform and ethyl acetate were recrystallized from 14 ml ethanol, giving 267 mg of 8-acetyl-7,8-dihydro-6,6-dimethyl-6H-[1,2,5]oxadiazolo[3,4-g][1,4]benzoxazine 3-oxide.

Workup

  1. additionwas further added dropwise
  2. stirringthe resulting mixture was stirred for ten minutes
  3. customTo the reaction mixture thus obtained
  4. stirringthe mixture was stirred for 90 minutes
  5. customthe precipitate which separated out
  6. filtrationwas collected by filtration, and its solution in 5 ml toluene
  7. temperaturewas heated
  8. temperatureunder reflux for eight hours
  9. additionThe reaction mixture was diluted with ethyl acetate
  10. dry with materialthe diluted solution was dried over anhydrous magnesium sulfate
  11. distillationthe solvents were distilled off from the dried solution
  12. customthe crystals obtained by elution with a 50:1 mixture of chloroform and ethyl acetate
  13. customwere recrystallized from 14 ml ethanol

Sources & evidence

ORD record
ord-2ae1d0f8cb1a44da82f26bc285b4f979
Source dataset
uspto-grants-1994_01
Patent number
US05278158

Reaction notes

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