Sodium Azide → HCID 86704519, compound

HRID 633425Notes

Reaction equation

HRID 633425 reaction equation
FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[Si:16]([O:23][CH2:24][C:25]1([CH2:39][O:40][Si:41]([C:44]([CH3:47])([CH3:46])[CH3:45])([CH3:43])[CH3:42])[O:30][C:29]2[CH:31]=[CH:32][C:33]([N+:35]([O-:37])=[O:36])=[CH:34][C:28]=2[NH:27][C:26]1=O)([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17].[N-:48]=[N+:49]=[N-:50].[Na+]>CC#N>[Si:41]([O:40][CH2:39][C:25]1([CH2:24][O:23][Si:16]([C:19]([CH3:20])([CH3:21])[CH3:22])([CH3:17])[CH3:18])[O:30][C:29]2[CH:31]=[CH:32][C:33]([N+:35]([O-:37])=[O:36])=[CH:34][C:28]=2[N:27]2[N:48]=[N:49][N:50]=[C:26]12)([C:44]([CH3:45])([CH3:46])[CH3:47])([CH3:43])[CH3:42]

Participants

5

Reactant 3

HCID 33557Sodium AzideHCID 67749Trifluoromethanesulfonic anhydrideHCID 86704520HCID 86704520, compound

Product 1

HCID 86704519HCID 86704519, compoundYield 49%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Trifluoromethanesulfonic anhydride (650 μL, 3.9 mmol) was added dropwise over 5 min to a stirred solution of 2,2-bis(((tert-butyldimethylsilyl)oxy)methyl)-6-nitro-2H-benzo[b][1,4]oxazin-3(4H)-one (0.62 g, 1.3 mmol) and NaN3 (0.50 g, 7.7 mmol) in MeCN (15 mL) at −10° C. (ice/MeOH bath) under nitrogen. The mixture was allowed to warm to room temperature slowly, then stirred at room temperature overnight. The mixture was then re-cooled to −10° C. and quenched by the addition of cold EtOAc (30 mL) followed by cold saturated NaHCO3 (30 mL) [note: saturated NaHCO3 solution was added over ca. 5 min]. Further EtOAc (50 mL) and H2O (30 mL) was added and the aqueous and organic layers were partitioned. The organic layer was dried (Na2SO4), filtered and the solvent removed under vacuum to leave a crude residue. The residue was dry-loaded on to silica gel and then purified by column chromatography on silica gel using hexane/DCM as eluent (1:0 to 0:1) to give the product (320 mg, 49% yield).

Workup

  1. temperatureThe mixture was then re-cooled to −10° C.
  2. customquenched by the addition of cold EtOAc (30 mL)
  3. customfollowed by cold saturated NaHCO3 (30 mL) [note: saturated NaHCO3 solution was added over ca. 5 min]
  4. additionFurther EtOAc (50 mL) and H2O (30 mL) was added
  5. customthe aqueous and organic layers were partitioned
  6. dry with materialThe organic layer was dried (Na2SO4)
  7. filtrationfiltered
  8. customthe solvent removed under vacuum
  9. customto leave a crude residue
  10. custompurified by column chromatography on silica gel

Sources & evidence

ORD record
ord-aaa0c6cf2be242d0b51c60840af79302
Source dataset
uspto-grants-2016_04
Patent number
US09321763B2

Reaction notes

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