Azidotrimethylsilane → 4,4-dimethyl-6-fluoro-8-nitro-4H-benzo[b]tetrazolo[1,5-d][1,4]oxazine

HRID 1754411Notes

Reaction equation

HRID 1754411 reaction equation
[F:1][C:2]1[C:7]2[O:8][C:9]([CH3:14])([CH3:13])[C:10](=S)[NH:11][C:6]=2[CH:5]=[C:4]([N+:15]([O-:17])=[O:16])[CH:3]=1.[Si]([N:22]=[N+:23]=[N-:24])(C)(C)C>C1COCC1.[Hg](OC(C)=O)OC(C)=O.CCOC(C)=O>[CH3:13][C:9]1([CH3:14])[O:8][C:7]2[C:2]([F:1])=[CH:3][C:4]([N+:15]([O-:17])=[O:16])=[CH:5][C:6]=2[N:11]2[N:22]=[N:23][N:24]=[C:10]12

Participants

6

Reactant 2

HCID 78378AzidotrimethylsilaneHCID 898638698-Fluoro-2,2-dimethyl-6-nitro-2H-benzo[b][1,4]oxazin-3(4H)-thione

Product 1

HCID 904376754,4-dimethyl-6-fluoro-8-nitro-4H-benzo[b]tetrazolo[1,5-d][1,4]oxazineYield 57%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 16683746DiacetyloxymercurySolvent

Procedure

To a solution of 8-fluoro-2,2-dimethyl-6-nitro-2H-benzo[b][1,4]oxazin-3(4H)-thione (1.0 g, 3.9 mmol) in THF, Hg(OAc)2 was added at 0° C. TMS-N3 was added to the reaction mixture at 0° C. and stirred for 1 hour. Reaction mixture was allowed to warm to room temperature and stirred for 3 hours. LCMS analysis of the reaction mixture indicated completion of the reaction. After 3 hours, the reaction mixture was diluted with 100 ml of EtOAc and partitioned with saturated aqueous NH4Cl (100 ml). Layers were separated and the aqueous layer was washed twice with EtOAc (50 ml). Combined EtOAc layers were dried over Na2SO4 and concentrated. The crude product was purified by column chromatography to give the product in 57% yield (0.57 g). LCMS (m/z) 266 (MH+).

Workup

  1. customReaction mixture
  2. stirringstirred for 3 hours
  3. customcompletion of the reaction
  4. waitAfter 3 hours
  5. custompartitioned with saturated aqueous NH4Cl (100 ml)
  6. customLayers were separated
  7. washthe aqueous layer was washed twice with EtOAc (50 ml)
  8. dry with materialCombined EtOAc layers were dried over Na2SO4
  9. concentrationconcentrated
  10. customThe crude product was purified by column chromatography
  11. customto give the product in 57% yield (0.57 g)

Sources & evidence

ORD record
ord-64653c725c894a67bae572ca25eba64f
Source dataset
uspto-grants-2015_10
Patent number
US09169249B2

Reaction notes

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