Reaction #40271

Reaction equation

potassium cyanide

ethyl cyanoacetate

isovaleraldehyde

hexane

potassium cyanide

→

2-isobutyl-succinonitrile

Yield 99.0%

Solvents

water

water

Conditions

Workup

1. 1
   OtherWhen no additional water was collected
2. 2
   Temperaturethe mixture was cooled
3. 3
   workup.DISTILLATIONdistilled under vacuum
4. 4
   Otherto remove solvent
5. 5
   workup.ADDITIONIsopropanol (1 L) was added to the remaining oil
6. 6
   workup.DISTILLATIONThe reaction mixture was distilled at atmospheric pressure until a temperature of 95° C.
7. 7
   Temperaturerefluxed at this temperature for 5 h
8. 8
   TemperatureThe reaction mixture was cooled
9. 9
   workup.ADDITIONdiluted with water (0.5 L)
10. 10
    Extractionextracted with 1 L methyl tert-butyl ether (MTBE)
11. 11
    ExtractionThe MTBE extract
12. 12
    Washwas washed with water (0.5 L)
13. 13
    Dryingdried over anhydrous magnesium sulfate
14. 14
    Filtrationfiltered
15. 15
    Concentrationconcentrated under vacuum

Procedure

A mixture of ethyl cyanoacetate (73.3 g, 6.48 mol), isovaleraldehyde (613.9 g, 7.13 mol), piperidine (5.5 g, 0.065 mol), and hexane (0.5 L) was placed under reflux with continuous removal of water. When no additional water was collected, the mixture was cooled and distilled under vacuum to remove solvent. Isopropanol (1 L) was added to the remaining oil, followed by a solution of potassium cyanide (422 g, 6.48 mol) in water (2 L). The reaction mixture was maintained below 35° C. during addition of the potassium cyanide solution and then held at approximately 35° C. for 4 h. The reaction mixture was distilled at atmospheric pressure until a temperature of 95° C. was reached and then refluxed at this temperature for 5 h. The reaction mixture was cooled, diluted with water (0.5 L) and extracted with 1 L methyl tert-butyl ether (MTBE). The MTBE extract was washed with water (0.5 L), dried over anhydrous magnesium sulfate, filtered, and concentrated under vacuum to give 873.4 g of 2-isobutyl-succinonitrile as an oil. Purified samples of 2-isobutyl-succinonitrile can be obtained by vacuum distillation (90° C. at 0.275 mm Hg).

Source