Ethyl cyanoacetate → 2-Cyano-hex-5-enoic acid ethyl ester

To a flamed dried flask charged with NaH (1.4 g, 35.46 mmol, 60% dispersion in mineral oil) and DMF (90 mL) equipped with a Firestone valve and under a stream of dry nitrogen was added, dropwise ethylcyanoacetate (3.14 mL, 29.56 mmol) over 20 min. The reaction mixture was then allowed to stir for 30 min, followed by addition of 4-bromobutene (3.0 mL, 29.56 mmol). The reaction mixture was allowed to stir overnight after which the solvent was removed by reduced pressure. The resulting crude mixture was dissolved in ethyl acetate, washed 3 times with 1N HCl solution and once with a saturated solution of brine. The organic and aqueous layers were separated and the organic layer was dried with sodium sulfate, filtered and the solvent was removed under reduced pressure to yield a residue. The residue was purified by flash chromatography using a mixture of 9:1 heptanes to ethyl acetate to yield a clear colorless oil.

1. customTo a flamed dried flask
2. customequipped with a Firestone valve and under a stream of dry nitrogen
3. additionwas added
4. stirringto stir overnight after which the solvent
5. customwas removed by reduced pressure
6. dissolutionThe resulting crude mixture was dissolved in ethyl acetate
7. washwashed 3 times with 1N HCl solution
8. customThe organic and aqueous layers were separated
9. dry with materialthe organic layer was dried with sodium sulfate
10. filtrationfiltered
11. customthe solvent was removed under reduced pressure
12. customto yield a residue
13. customThe residue was purified by flash chromatography
14. additiona mixture of 9:1 heptanes to ethyl acetate
15. customto yield a clear colorless oil

ORD record

ord-e7a1d9ae9c094e1e90c472ee0e233743

Source dataset

uspto-grants-2010_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07776882B2