Acetic Acid → N-(1,4-dioxaspiro[4.5]dec-8-yl)-1H-pyrazol-5-amine

HRID 2048629Notes

Reaction equation

HRID 2048629 reaction equation
C([N:8]1[C:12]([NH:13][CH:14]2[CH2:23][CH2:22][C:17]3([O:21][CH2:20][CH2:19][O:18]3)[CH2:16][CH2:15]2)=[CH:11][CH:10]=[N:9]1)C1C=CC=CC=1.C(O)(=O)C.C([O-])=O.[NH4+].C(OCC)(=O)C>C(O)C.[OH-].[Pd+2].[OH-]>[O:18]1[C:17]2([CH2:16][CH2:15][CH:14]([NH:13][C:12]3[NH:8][N:9]=[CH:10][CH:11]=3)[CH2:23][CH2:22]2)[O:21][CH2:20][CH2:19]1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 8857Ethyl AcetateHCID 2723923Ammonium formateHCID 670094261-benzyl-N-(1,4-dioxaspiro[4.5]dec-8-yl)-1H-pyrazol-5-amine

Product 1

HCID 67009993N-(1,4-dioxaspiro[4.5]dec-8-yl)-1H-pyrazol-5-amineYield 81.3%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

To a suspension of 1-benzyl-N-(1,4-dioxaspiro[4.5]dec-8-yl)-1H-pyrazol-5-amine (38 g) and palladium hydroxide (10 wt %, 11.4 g) in ethanol (200 mL)-acetic acid (40 mL) was added ammonium formate (32 g) by small portions at 80° C. After stirring at 80° C. for 4 hr, the mixture was allowed to cool to room temperature, ethyl acetate was added, and the insoluble material was filtered off. Saturated aqueous sodium hydrogen carbonate was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, and concentrated. The residue was crystallized using ethyl acetate, and the resulting solid was collected by filtration, washed with diisopropyl ether, and dried under reduced pressure to give the title compound as a pale-yellow solid (22 g, 81%).

Workup

  1. temperatureto cool to room temperature
  2. filtrationthe insoluble material was filtered off
  3. additionSaturated aqueous sodium hydrogen carbonate was added to the filtrate
  4. extractionthe mixture was extracted with ethyl acetate
  5. washThe organic layer was washed with water and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated
  8. customThe residue was crystallized
  9. filtrationthe resulting solid was collected by filtration
  10. washwashed with diisopropyl ether
  11. customdried under reduced pressure

Sources & evidence

ORD record
ord-aa9a91310b2840fe8c849c03b6cacd0b
Source dataset
uspto-grants-2013_11
Patent number
US08592431B2

Reaction notes

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