3-(3-methylfuran-2-yl)-3-oxopropanenitrile

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the method of Rudorf and Augustin (Phosphorus and Sulfur 1981, 9, 329), a solution of 4.4 g (29.5 mmol) 3-(3-methyl-furan-2-yl)-3-oxo-propionitrile in 30 ml dry DMSO was added dropwise to a stirred suspension of 2,4 g (59.0 mmol, 60% dispersion in mineral oil) sodium hydride in 20 ml DMSO under argon at room temperature. 1.8 ml (29.5 mmol) carbon disulfide was then added dropwise, with external water bath cooling, and stirring continued for 1 hour, after which 3.7 ml (59.0 mmol) methyl iodide was added dropwise, with external water bath cooling, and stirring continued for a further 16 h. The reaction mixture was then poured into 2 l ice-cold water, and the precipitate collected by filtration and dried in vacuo to afford 7.45 g (99%) 2-(3-methyl-furan-2-carbonyl)-3,3-bis-methylsulfanyl-acrylonitrile as a pale yellow crystalline solid. ES-MS m/e (%): 271 (M+NH4+, 33), 254 (M+H+, 100). cooling cooling stirring continued for a further 16 h the precipitate collected by filtration dried in vacuo

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the method of Turner and Jacks (J. Org. Chem. 1989, 54, 4229), to a stirred solution of 9.4 ml (179 mmol) acetonitrile in 250 ml dry THF under argon at −78° C. was added dropwise 78.9 ml (78.9 mmol) lithium bis(trimethylsilyl)amide solution (1M in THF) and stirring continued for 30 minutes, after which a solution of 5.0 g (35.7 mmol) methyl 3-methyl-2-furoate in 20 ml THF was added dropwise and stirring continued while the reaction mixture was allowed to warm slowly to −20° C. The reaction mixture was then cannulated into a rapidly stirred solution of 1M hydrochloric acid at 0° C. The mixtured was extracted twice with ether and the combined organic phases dried over sodium sulfate and concentrated in vacuo. Chromatography (ethyl acetate/hexane 1/4) afforded 4.43 g (83%) 3-(3-methyl-furan-2-yl)-3-oxo-propionitrile as a yellow crystalline solid. EI-MS m/e (%): 149 (M+, 20), 109 ([M—CH2CN]+, 100). stirring The mixtured was extracted twice with ether the combined organic phases dried over sodium sulfate concentrated in vacuo