Potassium Hydroxide → HCID 22140863, compound

HRID 2308083Notes

Reaction equation

HRID 2308083 reaction equation
[C:1]([C:3]1[CH:10]=[CH:9][C:6]([CH2:7]Br)=[CH:5][CH:4]=1)#[N:2].P(OCC)(OCC)[O:12]CC.O.Cl.[NH:23]1[CH2:28][CH2:27][C:26](=O)[CH2:25][CH2:24]1.[OH-].[K+]>CC(O)C.O.C(O)C.C1(C)C=CC=CC=1>[NH:23]1[CH2:28][CH2:27][C:26](=[CH:7][C:6]2[CH:9]=[CH:10][C:3]([C:1]([NH2:2])=[O:12])=[CH:4][CH:5]=2)[CH2:25][CH2:24]1

Participants

9

Reactant 4

HCID 14797Potassium HydroxideHCID 31215Triethyl phosphiteHCID 869964-(Bromomethyl)benzonitrileHCID 2723901Piperonylamine

Product 1

HCID 22140863HCID 22140863, compoundYield 41.4%

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolventHCID 3776IsopropanolSolvent

Procedure

4-Cyanobenzyl bromide (49.0 g, 250 mmol), triethyl phosphite (45.7 g, 275 mmol) and toluene (49 mL) were charged,and the mixture was stirred and heated under reflux for 3 hrs., while distilling away the solvent at normal pressure. Then, the mixture was allowed to return to room temperature and concentrated under reduced pressure to give a colorless transparent oil. 4-Piperidone hydrochloride monohydrate (46.1 g, 300 mmol), ethanol (350 mL) and potassium hydroxide (pellet, 70.1 g, 1250 mmol) were added successively, and the mixture was stirred at room temperature for 30 min. and at 65-70° C. for 4 hrs. to give a pale-yellow suspension. Water (0.5 L) was added to the suspension at 20-25° C., and the mixture was extracted with ethyl acetate (2.0 L) and ethyl acetate-ethanol (17:3, 2.0 L). The obtained organic layers were combined, washed with saturated brine (1.0 L) and concentrated under reduced pressure. To the resulting residue was added ethyl acetate (150 mL), and the mixture was stirred at 0-5° C. for 30 min. The crystals were collected by filtration and dried to give a pale-yellow solid. 2-Propanol (140 mL) was added thereto, and the mixture was stirred at room temperature for 30 min. and further at 0-5° C. for 30 min. The crystals were collected by filtration and dried to give the title compound (17.3 g, yield 41.4%) as pale-yellow crystals.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 3 hrs
  3. distillation, while distilling away the solvent at normal pressure
  4. customto return to room temperature
  5. concentrationconcentrated under reduced pressure
  6. customto give a colorless transparent oil
  7. stirringthe mixture was stirred at room temperature for 30 min. and at 65-70° C. for 4 hrs
  8. customto give a pale-yellow suspension
  9. extractionthe mixture was extracted with ethyl acetate (2.0 L) and ethyl acetate-ethanol (17:3, 2.0 L)
  10. washwashed with saturated brine (1.0 L)
  11. concentrationconcentrated under reduced pressure
  12. additionTo the resulting residue was added ethyl acetate (150 mL)
  13. stirringthe mixture was stirred at 0-5° C. for 30 min
  14. filtrationThe crystals were collected by filtration
  15. customdried
  16. customto give a pale-yellow solid
  17. stirringthe mixture was stirred at room temperature for 30 min. and further at 0-5° C. for 30 min
  18. filtrationThe crystals were collected by filtration
  19. customdried

Sources & evidence

ORD record
ord-b99603686b5f4f55aeb065115750bea3
Source dataset
uspto-grants-2004_12
Patent number
US06833457B1

Reaction notes

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