Ammonium formate → HCID 23353488, compound

HRID 235152Notes

Reaction equation

HRID 235152 reaction equation
[N+:1]([C:4]1[C:5]([NH:11][C:12]2[CH:21]=[C:20]3[C:15]([CH:16]=[CH:17][CH:18]=[C:19]3[N:22]3[CH2:27][CH2:26][N:25]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:24][CH2:23]3)=[CH:14][CH:13]=2)=[N+:6]([O-])[CH:7]=[CH:8][CH:9]=1)([O-])=O.C([O-])=O.[NH4+]>[Pd].C(O)C>[NH2:1][C:4]1[C:5]([NH:11][C:12]2[CH:21]=[C:20]3[C:15]([CH:16]=[CH:17][CH:18]=[C:19]3[N:22]3[CH2:27][CH2:26][N:25]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:24][CH2:23]3)=[CH:14][CH:13]=2)=[N:6][CH:7]=[CH:8][CH:9]=1

Participants

5

Reactant 2

HCID 2723923Ammonium formate2×HCID 178452224HCID 178452224, compound

Product 1

HCID 23353488HCID 23353488, compoundYield 30%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

A mixture of 7-(3-nitro-1-oxido-2-pyridylamino)-1-(4-tert-butoxycarbonyl-1-piperazinyl)-naphthalene (0.40 g, 0.86 mmol, product of the above reaction), ammonium formate (1.0 g, 17.2 mmol), and 10% palladium on carbon (0.15 g)in ethanol (30 mL) was refluxed 4 hour while continually returning sublimed ammonium formate back into the reaction. The solvent was removed at reduced pressure and the residue was taken up in methylene chloride. The organic solution was washed with water and brine, dried over calcium sulfate, and concentrated. The residue was flash chromatographed on silica gel (1×3 inches), Elution proceeded as follows: 25% ethyl acetate/hexane (100 mL), nil; 35% ethyl acetate/hexane (250 mL), 0.25 g of product. The product was treated with activated carbon, filtered, and concentrated. The residue was recrystallized from ethyl acetate/ether to give 0.11 g (30%) of 7-(3-amino-2-pyridylamino)-1-(4-tert-butoxycarbonyl-1-piperazinyl)-naphthalene as white crystals which were sensitive to air (turn brown on air exposure) and had mp 183°-184° C. Analysis calculated for C24H29N5O2 : C, 68.71; H, 6.97; N, 16.69. Found: C, 68.76; H, 6.58; N, 16.56.

Workup

  1. temperaturewas refluxed 4 hour
  2. customback into the reaction
  3. customThe solvent was removed at reduced pressure
  4. washThe organic solution was washed with water and brine
  5. dry with materialdried over calcium sulfate
  6. concentrationconcentrated
  7. customchromatographed on silica gel (1×3 inches), Elution
  8. additionThe product was treated with activated carbon
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was recrystallized from ethyl acetate/ether

Sources & evidence

ORD record
ord-aee32bf3f5df4509ad88cb6fb56fcb06
Source dataset
uspto-grants-1997_01
Patent number
US05597826

Reaction notes

Loading…