1,3-Dibromo-5,5-dimethylhydantoin → tert-Butyl 4-amino-4-methylpiperidine-1-carboxylate

HRID 451544Notes

Reaction equation

HRID 451544 reaction equation
[C:1]([C:4]1(C)[CH2:9][CH2:8][N:7]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:6][CH2:5]1)(=O)N.[OH-].[K+].Br[N:21]1C(C)(C)C(=O)N(Br)C1=O.S([O-])([O-])=O.[Na+].[Na+].[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C(#N)C.O.C(OCC)(=O)C>[NH2:21][C:4]1([CH3:1])[CH2:9][CH2:8][N:7]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:6][CH2:5]1

Participants

9

Reactant 5

HCID 64791,3-Dibromo-5,5-dimethylhydantoinHCID 14797Potassium HydroxideHCID 24437Sodium SulfiteHCID 62657Potassium Phosphate, TribasicHCID 53393793tert-Butyl 4-carbamoyl-4-methylpiperidine-1-carboxylate

Product 1

HCID 11310432tert-Butyl 4-amino-4-methylpiperidine-1-carboxylateYield 171.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of tert-butyl 4-carbamoyl-4-methylpiperidine-1-carboxylate (2.52 g, 10.4 mmol) in acetonitrile (7.6 mL) and water (23.4 mL) was added KOH (2.63 g, 46.8 mmol) at 0° C. Then 1,3-dibromo-5,5-dimethylhydantoin (1.64 g, 5.72 mmol) was added in one portion at 0° C. and after stirring at 0° C. for 30 minutes the solution was allowed to warm up to room temperature and stirred for 1 hour. Sodium sulfite (131 mg, 1.04 mmol) was added and the mixture was stirred for 15 minutes at room temperature, then ethyl acetate was added and the reaction was cooled to 10° C. K3PO4 (2.34 g, 11.0 mmol) was added and the mixture was warmed up to room temperature and extracted with ethyl acetate. The organic layers were washed with brine, dried over sodium sulfate, filtered and evaporated to give the title compound (2.1 g, 94%) as a colourless oil. MS ISP (m/e): 215.3 [(M+H)+].

Workup

  1. temperatureto warm up to room temperature
  2. stirringstirred for 1 hour
  3. stirringthe mixture was stirred for 15 minutes at room temperature
  4. temperaturethe reaction was cooled to 10° C
  5. temperaturethe mixture was warmed up to room temperature
  6. extractionextracted with ethyl acetate
  7. washThe organic layers were washed with brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-00e57d2f506a446e975bd0a2692a2dc3
Source dataset
uspto-grants-2013_07
Patent number
US08486967B2

Reaction notes

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