7-Fluoro-5-nitro-2,3-dihydrobenzo[b][1,4]dioxine → 7-Fluoro-2,3-dihydro-1,4-benzodioxin-5-amine

HRID 657014Notes

Reaction equation

HRID 657014 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([N+:12]([O-])=O)[C:5]2[O:10][CH2:9][CH2:8][O:7][C:6]=2[CH:11]=1.[H][H]>CO.[Pd]>[F:1][C:2]1[CH:3]=[C:4]([NH2:12])[C:5]2[O:10][CH2:9][CH2:8][O:7][C:6]=2[CH:11]=1

Participants

5

Reactant 2

HCID 688171507-Fluoro-5-nitro-2,3-dihydrobenzo[b][1,4]dioxineHCID 178418361HCID 178418361, compound

Product 1

HCID 666806007-Fluoro-2,3-dihydro-1,4-benzodioxin-5-amineYield 51%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

7-Fluoro-5-nitro-2,3-dihydro-1,4-benzodioxin (6.96 g, 35 mmol) and 5% Pd/C (4 g) in MeOH (500 ml) was stirred overnight in the presence of hydrogen at atmospheric pressure at rt. The catalyst was filtered off and solvent removed; the residue was dissolved in MeOH (100 ml), more 5% Pd/C (paste, 3 g) was added and mixture stirred overnight in presence of hydrogen (45 psi) at rt. The catalyst was filtered off and solvent removed; the residue treated with DCM (20 ml), the solid filtered off and compound in DCM loaded on silica (pre-wet with petroleum ether) and purified using a 10%-50% EtOAc: 40-60 petroleum ether gradient to provide the desired compound (3 g, 51%).

Workup

  1. filtrationThe catalyst was filtered off
  2. customsolvent removed
  3. dissolutionthe residue was dissolved in MeOH (100 ml)
  4. additionmore 5% Pd/C (paste, 3 g) was added
  5. filtrationThe catalyst was filtered off
  6. customsolvent removed
  7. additionthe residue treated with DCM (20 ml)
  8. filtrationthe solid filtered off
  9. custompurified

Sources & evidence

ORD record
ord-29fa6a16b93e4af7809c1d8cd7385257
Source dataset
uspto-grants-2011_12
Patent number
US08071592B2

Reaction notes

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