Dichloromethane → 2-Oxopiperidine-1-carbonitrile

HRID 223685Notes

Reaction equation

HRID 223685 reaction equation
[OH-].[Na+].[N:3]#[C:4][NH2:5].Cl[CH2:7][CH2:8][CH2:9][CH2:10][C:11](Cl)=[O:12].C(Cl)Cl>O>[C:4]([N:5]1[CH2:7][CH2:8][CH2:9][CH2:10][C:11]1=[O:12])#[N:3]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 9864Cyanamide2×HCID 14798Sodium HydroxideHCID 740895-Chlorovaleryl chloride

Product 1

HCID 205021192-Oxopiperidine-1-carbonitrileYield 47.8%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

59.4 g (1.484 moles) of sodium hydroxide are dissolved in 370 ml of water and the solution is cooled to 0° C. To this solution are added 13.2 g (0.742 mole) of cyanamide in portions. Then 115 g (0.742 mole) of δ-chlorovaleryl chloride are added dropwise, at 0°-8° C., over 1 hour to the clear, colourless cyanamide solution. The ensuing reaction is strongly exothermic, so that intensive cooling is necessary. When the dropwise addition is complete, the mixture is stirred for 1 hour at 0° C. Then 740 ml of methylene chloride are added and the reaction mixture is subsequently warmed for 1 hour to reflux temperature (40° C.). The two phases are separated in a separating funnel. The aqueous phase is extracted once more with 740 ml of methylene chloride. The combined organic phases are dried over sodium sulfate, filtered, and the solvent is removed in a water jet vacuum. Yield: 79.6 g (86.4% of theory). The crude product is a pale yellowish liquid which, according to gas chromatographic analysis, contains 79.95% of N-cyanopiperidone. An isomer is not detected. High vacuum distillation of the crude product yields 44 g (47.8% of theory) of N-cyanopiperidone as a pale yellowish liquid with a boiling point of 125° C./13.3 Pa. Gas chromatographic analysis shows the product to be 99.19% pure.

Workup

  1. customThe ensuing reaction
  2. temperatureso that intensive cooling
  3. additionWhen the dropwise addition
  4. temperaturethe reaction mixture is subsequently warmed for 1 hour
  5. temperatureto reflux temperature (40° C.)
  6. customThe two phases are separated in a separating funnel
  7. extractionThe aqueous phase is extracted once more with 740 ml of methylene chloride
  8. dry with materialThe combined organic phases are dried over sodium sulfate
  9. filtrationfiltered
  10. customthe solvent is removed in a water jet vacuum
  11. distillationHigh vacuum distillation of the crude product

Sources & evidence

ORD record
ord-65021793aa364e90b495d8488f043692
Source dataset
uspto-grants-1982_10
Patent number
US04356121

Reaction notes

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