Methyl Acrylate → dimethyl 4-cyano-4-phenylheptanedioate

HRID 1095490Notes

Reaction equation

HRID 1095490 reaction equation
[C:1]1([CH2:7][C:8]#[N:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:10]([O:14][CH3:15])(=[O:13])[CH:11]=[CH2:12]>C(O)(C)(C)C>[CH3:15][O:14][C:10](=[O:13])[CH2:11][CH2:12][C:7]([C:8]#[N:9])([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[CH2:12][CH2:11][C:10]([O:14][CH3:15])=[O:13]

Participants

4

Reactant 2

HCID 7294Methyl AcrylateHCID 8794Phenylacetonitrile

Product 1

HCID 283742dimethyl 4-cyano-4-phenylheptanedioate

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

Phenylacetonitrile (11.7 g, 0.1 mol) and methyl acrylate (47 ml, 0.5 mol) were initially introduced into tert-butanol (60 ml) and the mixture was heated to the boiling point. The heat source was then removed. Triton B (benzyltrimethylammonium hydroxide, 40 per cent in methanol, 15.2 ml), dissolved in tert-butanol (23 ml), was added dropwise, first slowly, later swiftly. After the dropwise addition, the mixture was boiled under reflux for 4 h. The reaction mixture was cooled to room temperature overnight.—For working up, toluene (100 ml) and water (70 ml) were added to the mixture. The organic phase was separated off and washed with water (1×70 ml) and saturated sodium chloride solution (1×50 ml). After drying with Na2SO4, the solvent was distilled off in a fume cupboard because of the severe odour nuisance. Purification was carried out by a bulb tube distillation under a pressure of 7.8×10−2 mbar at a temperature of 235° C. It was possible to isolate the desired 4-cyano-4-phenylheptanedioic acid dimethyl ester in a yield of 21.45 g (72%) as a colourless, viscous substance.

Workup

  1. temperaturethe mixture was heated to the boiling point
  2. customThe heat source was then removed
  3. dissolutionTriton B (benzyltrimethylammonium hydroxide, 40 per cent in methanol, 15.2 ml), dissolved in tert-butanol (23 ml)
  4. additionwas added dropwise
  5. additionAfter the dropwise addition
  6. temperatureunder reflux for 4 h
  7. additiontoluene (100 ml) and water (70 ml) were added to the mixture
  8. customThe organic phase was separated off
  9. washwashed with water (1×70 ml) and saturated sodium chloride solution (1×50 ml)
  10. dry with materialAfter drying with Na2SO4
  11. distillationthe solvent was distilled off in a fume cupboard because of the severe odour nuisance
  12. customPurification
  13. customwas carried out by a bulb tube
  14. distillationdistillation under a pressure of 7.8×10−2 mbar at a temperature of 235° C

Sources & evidence

ORD record
ord-98df2eecfb19434ab617901e905c5d5e
Source dataset
uspto-grants-2012_03
Patent number
US08138187B2

Reaction notes

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