Cyclodecanone → diethyl N-(1-cyclodecenyl)-aminomethylenemalonate

HRID 1761527Notes

Reaction equation

HRID 1761527 reaction equation
[C:1]1(=O)[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[NH2:12][CH:13]=[C:14]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:15]([O:17][CH2:18][CH3:19])=[O:16].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C(C)=CC=CC=1>[C:1]1([NH:12][CH:13]=[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH:2]=1

Participants

5

Reactant 3

HCID 73918CyclodecanoneHCID 226751Diethyl (aminomethylidene)propanedioateHCID 521998p-Toluenesulfonic acid monohydrate

Product 1

HCID 67906089diethyl N-(1-cyclodecenyl)-aminomethylenemalonate

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Procedure

A mixture of 25.0 g of cyclodecanone, 60.7 g of diethyl aminomethylenemalonate, 1.54 g of p-toluenesulfonic acid monohydrate in 500 ml xylene is refluxed 2 weeks under argon, collecting the distillate in a Dean-Stark trap. The solution is then decanted and solvent is removed. The residual oil is triturated twice with hexane and the combined hexane extract is concentrated to yield an oil which is flash chromatographed on 600 g of silica gel using 99:1 methylene chloride ethyl acetate as eluent. A forerun containing cyclodecanone is discarded and the fractions containing the product are combined and concentrated to dryness to give diethyl N-(1-cyclodecenyl)-aminomethylenemalonate as an oil.

Workup

  1. temperatureis refluxed 2 weeks under argon
  2. distillationcollecting the distillate in a Dean-Stark trap
  3. customThe solution is then decanted
  4. customsolvent is removed
  5. customThe residual oil is triturated twice with hexane
  6. extractionthe combined hexane extract
  7. concentrationis concentrated
  8. customto yield an oil which
  9. customchromatographed on 600 g of silica gel using 99:1 methylene chloride ethyl acetate as eluent
  10. additionA forerun containing cyclodecanone
  11. additionthe fractions containing the product
  12. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-192731807edd42b9ba01020ec4633ce5
Source dataset
uspto-grants-1989_05
Patent number
US04826854

Reaction notes

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