Methyl Acrylate → dimethyl 4-cyano-4-(4-fluorophenyl)heptanedioate

HRID 1576195Notes

Reaction equation

HRID 1576195 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]#[N:10])=[CH:4][CH:3]=1.[C:11]([O:15][CH3:16])(=[O:14])[CH:12]=[CH2:13]>C(O)(C)(C)C>[CH3:16][O:15][C:11](=[O:14])[CH2:12][CH2:13][C:8]([C:9]#[N:10])([C:5]1[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=1)[CH2:13][CH2:12][C:11]([O:15][CH3:16])=[O:14]

Participants

4

Reactant 2

HCID 7294Methyl AcrylateHCID 68016Benzeneacetonitrile, 4-fluoro-

Product 1

HCID 2781261dimethyl 4-cyano-4-(4-fluorophenyl)heptanedioateYield 72.2%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A mixture of 25 g. (0.185 mole) of the known compound p-fluorophenylacetonitrile and 86 ml. of methyl acrylate in 90 ml. of t-butyl alcohol is heated to reflux. The heat is removed and 28.1 ml. of 40% methanolic Triton B in 42 ml. of t-butyl alcohol quickly added. After about 4 hours of heating at reflux the mixture is allowed to cool and taken up in water and benzene. The organic layer is washed successively with 2.5 N hydrochloric acid, water and brine and then evaporated to dryness. The residue is distilled under vacuum, first at 40 mm. of mercury to remove methyl acrylate and then at 0.25 to 0.30 mm. to give 41 g. (72.2% yield) of dimethyl-4-cyano-4-(4-fluorophenyl)pimelate having a boiling point of 179° to 181°C. The NMR spectrum of the compound confirms its expected structure.

Workup

  1. additionA mixture of 25 g
  2. customThe heat is removed
  3. additionof t-butyl alcohol quickly added
  4. temperatureAfter about 4 hours of heating
  5. temperatureat reflux the mixture
  6. temperatureto cool
  7. washThe organic layer is washed successively with 2.5 N hydrochloric acid, water and brine
  8. customevaporated to dryness
  9. distillationThe residue is distilled under vacuum, first at 40 mm
  10. customof mercury to remove methyl acrylate
  11. customto give 41 g

Sources & evidence

ORD record
ord-7cf9691a96c946028fcd9589a7d02ae6
Source dataset
uspto-grants-1976_09
Patent number
US03979444

Reaction notes

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