Acetic Acid → TERT-BUTYL 4-(1-CYANO-2-ETHOXY-2-OXOETHYLIDENE)PIPERIDINE-1-CARBOXYLATE

HRID 2054455Notes

Reaction equation

HRID 2054455 reaction equation
[C:1]([CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].C([O-])(=O)C.[NH4+].C(O)(=O)C.O=[C:19]1[CH2:24][CH2:23][N:22]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:21][CH2:20]1>C1C=CC=CC=1.C(OCC)(=O)C.O>[C:1]([C:3](=[C:19]1[CH2:24][CH2:23][N:22]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:21][CH2:20]1)[C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 7764Ethyl cyanoacetateHCID 517165Ammonium AcetateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 11551073TERT-BUTYL 4-(1-CYANO-2-ETHOXY-2-OXOETHYLIDENE)PIPERIDINE-1-CARBOXYLATE

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

Ethyl cyanoacetate (11.0 mL, 126 mmol), ammonium acetate (0.976 g, 12.6 mmol) and acetic acid (0.715 mL, 12.6 mmol) were added to a solution of tert-butyl 4-oxopiperidine-1-carboxylate 8-1 (25.0 g, 126 mmol) in 200 mL of benzene at ambient temperature. After stirring at reflux with azeotropic removal of water (Dean-Stark apparatus), the reaction mixture was cooled to ambient temperature and diluted with ethyl acetate (500 mL). The organics were washed with saturated aqueous sodium bicarbonate, brine, dried (magnesium sulfate), and concentrated in vacuo to give a crude residue. Purification of the crude residue by recrystallization from 10% ethyl acetate/hexanes afforded 8-2 as a white crystalline solid.

Workup

  1. washThe organics were washed with saturated aqueous sodium bicarbonate, brine
  2. dry with materialdried (magnesium sulfate)
  3. concentrationconcentrated in vacuo
  4. customto give a crude residue
  5. customPurification of the crude residue
  6. customby recrystallization from 10% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-8c41c1eaa8ec485a91e8bd312e56cf16
Source dataset
uspto-grants-2008_02
Patent number
US07329673B2

Reaction notes

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