Sodium Carbonate → 3,6-Bis-allyloxybenzo[d]isoxazol-5-ylamine

HRID 643935Notes

Reaction equation

HRID 643935 reaction equation
[CH2:1]([O:4][C:5]1[C:9]2[CH:10]=[C:11]([N+:18]([O-])=O)[C:12]([O:14][CH2:15][CH:16]=[CH2:17])=[CH:13][C:8]=2[O:7][N:6]=1)[CH:2]=[CH2:3].O.O.[Sn](Cl)Cl.C(=O)([O-])[O-].[Na+].[Na+]>CCOC(C)=O.C([O-])(O)=O.[Na+]>[CH2:1]([O:4][C:5]1[C:9]2[CH:10]=[C:11]([NH2:18])[C:12]([O:14][CH2:15][CH:16]=[CH2:17])=[CH:13][C:8]=2[O:7][N:6]=1)[CH:2]=[CH2:3]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 61436Stannous chloride dihydrateHCID 667509873,6-Bis-allyloxy-5-nitrobenzo[d]isoxazole

Product 1

HCID 667507363,6-Bis-allyloxybenzo[d]isoxazol-5-ylamine

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolvent2×HCID 516892Sodium BicarbonateSolvent

Procedure

To a solution of 3,6-bis-allyloxy-5-nitrobenzo[d]isoxazole (0.60 g, 2.17 mmol) in EtOAc (12 mL) is added portionwise tin(II) chloride dihydrate (2.2 g, 9.75 mmol). The mixture is stirred at room temperature for 2 h and then at 60° C. for 1.5 h. The mixture is diluted with EtOAc and saturated NaHCO3 is added dropwise, resulting in the formation of a precipitate. Sodium carbonate (2N) is added and the insoluble precipitate is filtered off. The phases are separated and the aqueous phase is extracted with EtOAc (3×). The organic layers are washed with water and brine, dried over MgSO4, filtered and concentrated. The crude material is purified by flash chromatography on silica gel, eluting with a gradient of hexanes/EtOAc to afford 3,6-bis-allyloxybenzo[d]isoxazol-5-ylamine as a waxy solid: (M+H)+=247.2.

Workup

  1. waitat 60° C. for 1.5 h
  2. additionis added dropwise
  3. customresulting in the formation of a precipitate
  4. filtrationthe insoluble precipitate is filtered off
  5. customThe phases are separated
  6. extractionthe aqueous phase is extracted with EtOAc (3×)
  7. washThe organic layers are washed with water and brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude material is purified by flash chromatography on silica gel
  12. washeluting with a gradient of hexanes/EtOAc

Sources & evidence

ORD record
ord-b371f8089b2e4c2893e062e366e6ce1d
Source dataset
uspto-grants-2010_04
Patent number
US07700633B2

Reaction notes

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