[P].[S].[C:3]([CH2:5][C:6]([C:8]1[O:12][C:11]([C:13]#[N:14])=[CH:10][CH:9]=1)=[O:7])#[N:4].[H-].[Na+].[C:17](=S)=[S:18].CI.[CH3:22][S:23]([CH3:25])=O>>[C:3]([C:5](=[C:22]([S:18][CH3:17])[S:23][CH3:25])[C:6]([C:8]1[O:12][C:11]([C:13]#[N:14])=[CH:10][CH:9]=1)=[O:7])#[N:4]Following the method of Rudorf and Augustin (Phosphorus and Sulfur 1981, 9, 329), a solution of 2.90 g (18.1 mmol) 5-cyanoacetyl-furan-2-carbonitrile in 10 ml dry DMSO was added dropwise to a stirred suspension of 1.45 g (36.2 mmol, 60% dispersion in mineral oil) sodium hydride in 10 ml DMSO under argon at room temperature. 1.09 ml (18.1 mmol) carbon disulfide was then added dropwise, with external water bath cooling, and stirring continued for 2 hour, after which 2.26 ml (36.2 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 1 l ice-cold water, and the precipitate collected by filtration, washed with hexane, and dried in vacuo to afford 3,50 g (73%) 5-(2-cyano-3,3-bis-methylsulfanyl-acryloyl)-furan-2-carbonitrile as a green crystalline solid. EI-MS m/e (%): 264 (M+, 25), 263 ([M—H]+, 30), 249 ([M—CH3]+, 40), 195 (37), 120 (100).
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