Ammonium Chloride → tert-Butyl 6-oxo-2-azaspiro(3.3)heptane-2-carboxylate

HRID 336542Notes

Reaction equation

HRID 336542 reaction equation
[Cl-].[NH4+].Cl[C:4]1(Cl)[C:17](=[O:18])[CH2:16][C:5]21[CH2:8][N:7]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:6]2>CO.O.[Zn]>[O:18]=[C:17]1[CH2:4][C:5]2([CH2:6][N:7]([C:9]([O:11][C:12]([CH3:14])([CH3:13])[CH3:15])=[O:10])[CH2:8]2)[CH2:16]1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 69669942tert-Butyl 5,5-dichloro-6-oxo-2-azaspiro[3.3]heptane-2-carboxylate

Product 1

HCID 52333005tert-Butyl 6-oxo-2-azaspiro(3.3)heptane-2-carboxylateYield 17.9%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

15.13 g (0.283 mmol) of ammonium chloride are added to a solution containing 13.21 g (47.15 mmol) of tert-butyl 5,5-dichloro-6-oxo-2-azaspiro[3.3]heptane-2-carboxylate, obtained in the preceding step, in 250 mL of methanol. The reaction medium is cooled with the aid of an ice/water bath, and 30.83 g (0.471 mmol) of zinc are added. After stirring at room temperature for 12 hours, the Celite is filtered off and rinsed with methanol. The filtrate is evaporated to dryness. The residue obtained is taken up in water and extracted several times with ethyl acetate. The combined organic phases are dried over sodium sulfate and the filtrate is concentrated under reduced pressure. After evaporating off the solvent, the residue obtained is purified by chromatography on silica gel, eluting with a 90/10 mixture of cyclohexane and ethyl acetate. 1.78 g of pure product are thus obtained in the form of a white powder.

Workup

  1. temperatureThe reaction medium is cooled with the aid of an ice/water bath
  2. filtrationthe Celite is filtered off
  3. washrinsed with methanol
  4. customThe filtrate is evaporated to dryness
  5. customThe residue obtained
  6. extractionextracted several times with ethyl acetate
  7. dry with materialThe combined organic phases are dried over sodium sulfate
  8. concentrationthe filtrate is concentrated under reduced pressure
  9. customAfter evaporating off the solvent
  10. customthe residue obtained
  11. customis purified by chromatography on silica gel
  12. washeluting with a 90/10 mixture of cyclohexane and ethyl acetate

Sources & evidence

ORD record
ord-8c88c5fbba894e5d84d9b7027a37e242
Source dataset
uspto-grants-2014_11
Patent number
US08889702B2

Reaction notes

Loading…