Nitrogen → Methyl 3-(1-cyanoethyl)benzoate

HRID 1198002Notes

Reaction equation

HRID 1198002 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]([CH2:11][C:12]#[N:13])[CH:8]=[CH:9][CH:10]=1)=[O:4].[C:14](=O)(OC)OC.C([O-])([O-])=O.[K+].[K+].N#N>>[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]([CH:11]([CH3:14])[C:12]#[N:13])[CH:8]=[CH:9][CH:10]=1)=[O:4]

Participants

5

Reactant 4

HCID 947NitrogenHCID 11430Potassium Carbonate2×HCID 12021Dimethyl CarbonateHCID 10821136Methyl 3-(cyanomethyl)benzoate

Product 1

HCID 10035402Methyl 3-(1-cyanoethyl)benzoateYield 78%

Conditions

Temperature
180 °C

Procedure

The reaction for the selective methylation is carried out placing into a 250 ml (φi =45 mm) stainless steel autoclave a mixture of (3-methoxycarbonylphenyl)acetonitrile (10 g, 96% purity), dimethyl carbonate (86 ml) and K2CO3 (12 g), in the 1:18:2 molar ratio. Air is replaced by a N2 stream; then the mixture is heated at a temperature of 180° C., with stirring. During the reaction, which is completed within 6 hours, the pressure raises from 7 bars, reached at the working temperature, to about 12 bars after 5 hours of isothermal heating. After cooling K2CO3 is filtered off, DMC is recovered and the residue is distilled (b.p. 0.078=109°-110° C.) to obtain 8.3 g of 2-(3-methoxycarbonyl-phenyl)propionitrile which is 99,5% pure (78% yield) (>99% selectivity in monomethylation).

Workup

  1. customThe reaction for the selective methylation
  2. customDuring the reaction, which
  3. temperaturethe pressure raises from 7 bars
  4. waitreached at the working temperature, to about 12 bars after 5 hours of isothermal heating
  5. filtrationis filtered off
  6. customDMC is recovered
  7. distillationthe residue is distilled (b.p. 0.078=109°-110° C.)

Sources & evidence

ORD record
ord-e930f9b8a13e448998fa6de531f35d7b
Source dataset
uspto-grants-1994_01
Patent number
US05278333

Reaction notes

Loading…