Ethyl 2-(2-cyanoethyl)acetoacetate ethyleneketal → HCID 20233222, compound

HRID 65486Notes

Reaction equation

HRID 65486 reaction equation
[CH2:1]1[O:16][C:4]([CH3:15])([CH:5]([CH2:11][CH2:12][C:13]#[N:14])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[O:3][CH2:2]1>[Rh].N>[CH2:2]1[O:3][C:4]([CH3:15])([CH:5]([CH2:11][CH2:12][CH2:13][NH2:14])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[O:16][CH2:1]1

Participants

4

Reactant 1

HCID 20233216Ethyl 2-(2-cyanoethyl)acetoacetate ethyleneketal

Product 1

HCID 20233222HCID 20233222, compound

Reagents, catalysts & solvents 2

HCID 23948RhodiumCatalyst2×HCID 222AmmoniaSolvent

Procedure

The above ketal was hydrogenated over a rhodium-on-alumina catalyst as follows: After dissolving 16 g of ethyl 2-(2-cyanoethyl)acetoacetate ethyleneketal in 90 ml of 10% ethanolic ammonia, 2 g of 5% rhodium-on-alumina were added, and the mixture hydrogenated at low pressure. The catalyst was separated by filtration, and the solvent removed from the filtrate to yield, as a residue, ethyl 2-(3-aminopropyl)acetoacetate ethyleneketal formed in the above hydrogenation. NMR indicated a mixture of the expected ketal plus some cyclized product produced by the next reaction step. The crude product from the above reaction was therefore heated in toluene solution for about 2 hours to convert the amino derivative to 3-acetyl-2-piperidone ethyleneketal. NMR showed the reaction being incomplete at this point; heating in toluene was therefore continued for 7 more hours. NMR again showed incomplete reaction; so heating was continued overnight. After a total of 24 hours of heating under reflux, the reaction mixture was cooled, and the solvent was removed in vacuo.

Workup

  1. additionwere added
  2. customThe catalyst was separated by filtration
  3. customthe solvent removed from the filtrate
  4. customto yield, as a residue

Sources & evidence

ORD record
ord-6b8b1d3b79a64e8cb1376846298f0b3b
Source dataset
uspto-grants-1986_09
Patent number
US04614807

Reaction notes

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