Acrylonitrile → 3-(4-Methoxyphenoxy)propanenitrile

Temperature

80 °C

4-Methoxyphenol (263.0 g) was dissolved in acrylonitrile (224.8 g), and then Triton B (18 mL) was added dropwise at room temperature, with stirring at 80° C. for 48 hours. The reaction liquor was returned to room temperature while slowly stirring, and stirred for 12 hours. The reaction liquor was further left to stand at 6° C. to precipitate white prisms. The mother liquor was subjected to decantation, and cold toluene (300 mL) was added to obtain crystals, and then the resulting crude crystals were dried at room temperature under reduced pressure (3 hours) (crude crystals 232.6 g). The crude crystals were dissolved in ethyl acetate (250 mL) at 50° C., n-heptane (250 mL) was slowly added with stirring, and the resulting mixture was recrystallized with slow stirring for 12 hours. The mother liquor was subjected to decantation, n-heptane (300 mL) was added, and crystals were obtained. The crystals were washed with n-heptane (400 mL) and dried at room temperature under reduced pressure (crystal No. 1: white prisms 154.5 g). Since crystals were generated in the mother liquor, pale yellow prisms were obtained as crystal No. 2 (crystal No. 2: pale yellow prisms 56.1 g). All of the filtrate and n-heptane used for washing were recovered and concentrated under reduced pressure. Then, toluene (500 mL) was added to the residue, and the mixture was washed with 1 N aqueous sodium hydroxide solution (100 mL×3 times), water (500 mL), 1 N aqueous hydrochloric acid solution (100 mL×3 times), water (500 mL) and saturated brine (300 mL), then dried over anhydrous sodium sulfate for 30 minutes, and filtered, and subsequently the filtrate was concentrated under reduced. The residue was dissolved in ethyl acetate (150 mL) at 50° C., and n-heptane (150 mL) was slowly added with stirring, and the resulting mixture was recrystallized with slow stirring for 12 hours. The mother liquor was subjected to decantation, and n-heptane (200 mL) was added, and crystals were obtained. The crystals were washed with n-heptane (300 mL) and dried at room temperature under reduced pressure (crystal No. 3: white prisms 59.0 g). Furthermore, pale yellow prisms were obtained as crystal No. 4 (crystal No. 4: 19.0 g). Total amount obtained was 288.6 g, yield was 76.9%+ crude crystals (yellow prisms, 21.8 g, 5.8%).

1. additionTriton B (18 mL) was added dropwise at room temperature
2. customwas returned to room temperature
3. stirringwhile slowly stirring
4. stirringstirred for 12 hours
5. waitThe reaction liquor was further left
6. customto stand at 6° C.
7. customto precipitate white prisms
8. additionwas added
9. customto obtain crystals
10. dry with materialthe resulting crude crystals were dried at room temperature under reduced pressure (3 hours) (crude crystals 232.6 g)
11. dissolutionThe crude crystals were dissolved in ethyl acetate (250 mL) at 50° C.
12. additionn-heptane (250 mL) was slowly added
13. stirringwith stirring
14. customthe resulting mixture was recrystallized
15. stirringwith slow stirring for 12 hours
16. additionwas added
17. customcrystals were obtained
18. washThe crystals were washed with n-heptane (400 mL)
19. dry with materialdried at room temperature under reduced pressure (crystal No. 1: white prisms 154.5 g)
20. custompale yellow prisms were obtained as crystal No
21. washfor washing
22. customwere recovered
23. concentrationconcentrated under reduced pressure
24. additionThen, toluene (500 mL) was added to the residue
25. washthe mixture was washed with 1 N aqueous sodium hydroxide solution (100 mL×3 times), water (500 mL), 1 N aqueous hydrochloric acid solution (100 mL×3 times), water (500 mL) and saturated brine (300 mL)
26. dry with materialdried over anhydrous sodium sulfate for 30 minutes
27. filtrationfiltered
28. concentrationsubsequently the filtrate was concentrated
29. dissolutionThe residue was dissolved in ethyl acetate (150 mL) at 50° C.
30. additionn-heptane (150 mL) was slowly added
31. stirringwith stirring
32. customthe resulting mixture was recrystallized
33. stirringwith slow stirring for 12 hours
34. additionwas added
35. customcrystals were obtained
36. washThe crystals were washed with n-heptane (300 mL)
37. dry with materialdried at room temperature under reduced pressure (crystal No. 3: white prisms 59.0 g)
38. customFurthermore, pale yellow prisms were obtained as crystal No
39. customTotal amount obtained

ORD record

ord-6197b9ff6b3c4066b99cae45895cae36

Source dataset

uspto-grants-2010_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07790903B2