Acrylonitrile → HCID 11819726, compound

Namely, to a solution of 50 ml (0.35 mol) of ethyl cyclopentanone-2-carboxylate in 130 ml of dioxane was added 3.8 ml of Triton B. Then, to the solution was added 27.1 ml (0.242 mol) of acrylonitrile in 50 ml of dioxane. The solution was stirred at room temperature for 12 hours, and extracted with ether after 100 ml of 10% hydrochloric acid was added thereto. An organic layer was dried over anhydrous magnesium silfate. After removinq the solvent, 300 ml of conc. hydrochloric acid was added to the residue and the mixture was heated under reflux for 24 hours. After cooling, the mixture was extracted with ether and 5% aqueous solution of sodium hydroxide was added to the ether layer and the mixture was stirred. An aqueous layer was made acidic with addition of 10% hydrochloric acid, and then the mixture was extracted with ethyl acetate. An organic layer was dried over anhydrous magnesium sulfate. After removing the solvent, the residue was dissolved in 150 ml of ethanol and 10 ml of conc. sulfuric acid was added thereto. The mixture was heated under reflux for 14 hours, and then ethanol was removed therefrom after cooling, and ethyl acetate was added thereto. The mixture was washed with 10% aqueous solution of sodium hydroxide and dried over anhydrous magnesium sulfate. After removing the solvent, the resulting residue was chromatographed over silica gel to obtain 45 g (yield 70%) of ethyl 2-oxocyclopentanepropionate from hexane-ethyl acetate (4:1) eluate. In 150 ml of 80% ethanol was dissolved 5.5 g (30 mmol) of this compound. To the solution were added 4.17 g (60 mmol) of hydroxylamine hydrochloride and 2.7 g (33 mmol) of sodium acetate and the mixture was stirred at room temperature over night. After removing ethanol, the mixture was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. After removing the solvent, the resulting residue was chromatographed over silica gel to obtain 5 g (yield 84% ) of ethyl 2-hydroxyiminocyclopentanepropionate from hexane-ethyl acetate (6:1) eluate. In 15 ml of anhydrous ethanol was dissolved 4.4 g of this compound and the solution was stirred at 50° C. for 4 hours under a hydrogen pressure of 120 atm. with use of Raney nickel (W2) as a catalyst. After removing Raney nickel by filtration and removing the solvent, the resulting residue was chromatographed over silica gel to obtain 0.95 g (yield 31%) of 2-azabicyclo[4.3.0]nonane-3-one from ethyl acetate eluate.

1. extractionextracted with ether after 100 ml of 10% hydrochloric acid
2. additionwas added
3. dry with materialAn organic layer was dried over anhydrous magnesium silfate
4. additionwas added to the residue
5. temperaturethe mixture was heated
6. temperatureunder reflux for 24 hours
7. temperatureAfter cooling
8. extractionthe mixture was extracted with ether and 5% aqueous solution of sodium hydroxide
9. additionwas added to the ether layer
10. stirringthe mixture was stirred
11. additionAn aqueous layer was made acidic with addition of 10% hydrochloric acid
12. extractionthe mixture was extracted with ethyl acetate
13. dry with materialAn organic layer was dried over anhydrous magnesium sulfate
14. customAfter removing the solvent
15. dissolutionthe residue was dissolved in 150 ml of ethanol
16. addition10 ml of conc. sulfuric acid was added
17. temperatureThe mixture was heated
18. temperatureunder reflux for 14 hours
19. customethanol was removed
20. temperatureafter cooling
21. additionethyl acetate was added
22. washThe mixture was washed with 10% aqueous solution of sodium hydroxide
23. dry with materialdried over anhydrous magnesium sulfate
24. customAfter removing the solvent
25. customthe resulting residue was chromatographed over silica gel

ORD record

ord-52546dcd8b8546cfac9557f516d05a78

Source dataset

uspto-grants-2002_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06500819B2