Acrylonitrile → 4-oxo-4-pyridin-4-ylbutanenitrile

C-1. 4-Oxo-4-(4-pyridinyl)butanenitrile--To a stirred mixture containing 29.4 g. of sodium cyanide and 500 ml. of acetonitrile, after stirring said mixture for ten minutes, was added dropwise over a period of three hours a solution containing 64.2 g. of 4-pyridinecarboxaldehyde in 500 ml. of acetonitrile and the resulting mixture was stirred at room temperature for one hour. To the stirred mixture was added slowly over a period of one hour a solution of 24.5 g. of acrylonitrile in 200 ml. of acetonitrile and the resulting reaction mixture was stirred overnight at room temperature. The reaction mixture was stripped in vacuo of solvent at a temperature not exceeding 54° C. The semi-solid residue was cooled, mixed well with 400 ml. of chloroform, and the mixture filtered. The chloroform was distilled off in vacuo at a temperature not exceeding 50° C. and the residual oily residue was extracted with three 200 ml. portions of toluene. The toluene solution was filtered through diatomaceous earth and the filtrate was distilled in vacuo below 50° C. to remove the toluene. The residue on chilling crystallized. A tiny sample was saved and the remainder was dissolved in 50 ml. of warm isopropyl alcohol. The solution was cooled and then diluted slowly with 125 ml. of ether, chilled and seeded with a crystal obtained from said tiny sample. The crystalline product that separated was collected, washed with 25 ml. of 1:3 (v:v) mixture of isopropyl alcohol:ether, and air-dried to yield 52.1 g of 4-oxo-4-(4-pyridinyl)butanenitrile, m.p. 53.5°-55° C.

1. customfor ten minutes
2. additionwas added dropwise over a period of three hours a solution
3. additioncontaining 64.2 g
4. additionTo the stirred mixture was added slowly over a period of one hour a solution of 24.5 g
5. customexceeding 54° C
6. temperatureThe semi-solid residue was cooled
7. additionmixed well with 400 ml
8. filtrationof chloroform, and the mixture filtered
9. distillationThe chloroform was distilled off in vacuo at a temperature not
10. customexceeding 50° C.
11. extractionthe residual oily residue was extracted with three 200 ml
12. filtrationThe toluene solution was filtered through diatomaceous earth
13. distillationthe filtrate was distilled in vacuo below 50° C.
14. customto remove the toluene
15. temperatureThe residue on chilling
16. customcrystallized
17. dissolutionthe remainder was dissolved in 50 ml
18. temperatureThe solution was cooled
19. additiondiluted slowly with 125 ml
20. temperatureof ether, chilled
21. customobtained
22. customThe crystalline product that separated
23. customwas collected
24. washwashed with 25 ml
25. additionof 1:3 (v:v) mixture of isopropyl alcohol
26. dry with materialether, and air-dried

ORD record

ord-60c1346b4fc94d3386aecd7589803cf3

Source dataset

uspto-grants-1981_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04304777