Abstract
2-Alkylidenethiazolidine-4,5-diones and 2-alkylideneoxazolidine-4,5-diones have been prepared by one-pot cyclization of arylacetonitriles with heterocumulenes and ethyl 2-chloro-2-oxoacetate.
Key words
one-pot cyclization - arylacetonitriles - heterocumulenes
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Typical Experimental Procedure: To a THF solution (10 mL) of 1a (0.234 g, 2.0 mmol) was added n -butyllithium (0.24 mL, 4.4 mmol, 1.6 M) at 0 °C. After stirring for 1 h, 2a (0.270 g, 2.0 mmol) was added and the solution was stirred for 1 h at 0 °C. Subsequently, 3a (0.241 g, 2.0 mmol) was added. After warming of the solution to 20 °C during 16 h, an aqueous solution of HCl (30 mL, 1 M) was added. The organic and the aqueous layer were separated and the latter was extracted with EtOAc (3 ¥ 30 mL). The combined organic layers were extracted with brine (30 mL), dried (Na2 SO4 ), filtered and the solvent of the filtrate was removed in vacuo. The residue was purified by column chromatography (silica gel, n -hexane-EtOAc = 5:1) to give 4a as a yellow solid (0.358 g, 58 %). Spectroscopic data of 4a : 1 H NMR (300 MHz, CDCl3 ): δ = 7.37-7.41 (m, 3 H, Ph), 7.43-7.51 (m, 4 H, Ph), 7.63-7.69 (m, 3 H, Ph). 13 C NMR (75 MHz, CDCl3 ): δ = 94.42, 113.50 (C), 126.65, 128.37, 129.37, 129.88, 130.10, 131.36 (CH), 140.43, 143.23, 156.40, 178.50 (C). IR (KBr): ν = 2193 (w), 1739 (s), 1591 (s), 1492 (s), 1444 (w) cm-1 . MS (EI, 70eV): m/z (%) = 306 (27) [M+ ], 218 (33), 159 (100), 114 (16), 88 (9). Anal. Calcd for C17 H10 N2 O2 S: C, 66.65; H, 3.29; N, 9.14. Found: C, 66.85; H, 3.02; N, 8.97.