Ammonia → 2,4-Dioxo-3-azaspiro(5.5)undecane-1,5-dicarbonitrile

HRID 1446373Notes

Reaction equation

HRID 1446373 reaction equation
[C:1]1(=O)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[C:8]([CH2:10][C:11]([O:13]CC)=O)#[N:9].[NH3:16].S(=O)(=O)(O)O.[OH2:22]>CO>[C:11]([CH:10]1[C:1]2([CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]2)[CH:10]([C:8]#[N:9])[C:11](=[O:13])[NH:9][C:8]1=[O:22])#[N:16]

Participants

7

Reactant 5

HCID 222Ammonia4×HCID 962Water2×HCID 1118Sulfuric AcidHCID 7764Ethyl cyanoacetateHCID 7967Cyclohexanone

Product 1

HCID 203662,4-Dioxo-3-azaspiro(5.5)undecane-1,5-dicarbonitrileYield 85%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Conditions

Temperature
7.5 °C

Procedure

98 g (1 mol) of cyclohexanone, 226 g (2 mol) of ethyl cyanoacetate, and 392 g of 96% methanol were mixed in a reaction flask, to which 272 g of aqueous ammonia (equivalent to 4 mol of ammonia gas) was added under stirring. Specifically, to carry out the addition of aqueous ammonia, the temperature was lowered to within the range of −5° C. to 0° C., ¾ of the prescribed amount of aqueous ammonia was added dropwise, the reaction mixture was then stirred for a first 12 hours with the temperature maintained at −5° C. to 0° C., and a second 12 hours with the temperature maintained at 5 to 10° C., and then the rest ¼ of aqueous ammonia was added. The reaction mixture was heated to and maintained at 20° C. to 25° C. for 24 hours under stirring. The mixture was then heated to 60° C., to which water was added in an amount equivalent to methanol, that is, 980 g water was added. The pH value was adjusted to 2-3 with dropwise addition of sulfuric acid, after which the temperature was lowered to below 5° C. and the mixture was centrifugally filtered. The filter cake was washed with water to pH 6-7, filtered, and dried to provide 1,5-dicyano-2,4-dioxo-3-azaspiro[5,5]-undecane. Yield: 85%, melting point: 202-210° C.

Workup

  1. additionwas added
  2. additionwas added dropwise
  3. stirringthe reaction mixture was then stirred for a first 12 hours with the temperature
  4. temperaturemaintained at −5° C. to 0° C.
  5. temperatureThe reaction mixture was heated to and
  6. temperaturemaintained at 20° C. to 25° C. for 24 hours
  7. stirringunder stirring
  8. customwas lowered to below 5° C.
  9. filtrationthe mixture was centrifugally filtered
  10. washThe filter cake was washed with water to pH 6-7
  11. filtrationfiltered
  12. customdried

Sources & evidence

ORD record
ord-05bc5660ee4144cd9cc355a0715cd705
Source dataset
uspto-grants-2010_02
Patent number
US07667071B2

Reaction notes

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