Ethyl cyanoacetate → Ethyl 2-cyano-2-cyclopentylideneacetate

HRID 1397504Notes

Reaction equation

C[Si](C)(C)N[Si](C)(C)C.[C:10]1(=O)[CH2:14][CH2:13][CH2:12][CH2:11]1.[C:16]([CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])#[N:17]>C(O)(=O)C.O.C(OCC)(=O)C>[C:16]([C:18](=[C:10]1[CH2:14][CH2:13][CH2:12][CH2:11]1)[C:19]([O:21][CH2:22][CH3:23])=[O:20])#[N:17]

Participants

Conditions

Temperature: 70 °C

Procedure

To an ambient solution of hexamethyldisilazane (17.7 mL, 84.0 mmol) in acetic acid (56 mL) was added sequentially cyclopentanone (5.0 mL, 56.3 mmol) and ethyl 2-cyanoacetate (12.0 mL, 113 mmol). The solution was heated to 70° C. for 15 hours. The reaction was cooled to room temperature and diluted with water (100 mL) and ethyl acetate (100 mL). The layers were separated, and the aqueous was extracted with additional ethyl acetate (2×100 mL). The combined organics were dried with anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by chromatography on SiO2 gel, eluting with 100% hexane to 5% ethyl acetate in hexane, to give the title product as a white, solid. MS (ESI) m/z 180 [M+H]+.

Workup

temperatureThe reaction was cooled to room temperature
customThe layers were separated
extractionthe aqueous was extracted with additional ethyl acetate (2×100 mL)
dry with materialThe combined organics were dried with anhydrous Na2SO4
filtrationfiltered
concentrationconcentrated under reduced pressure
customThe residue was purified by chromatography on SiO2 gel
washeluting with 100% hexane to 5% ethyl acetate in hexane

Sources & evidence

ORD record: ord-60c1d91605664d369f9d83c0bc6b1aeb
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08901152B2

Reaction notes

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