Synthesis of 2-Alkylidenethiazolidine-4,5-diones and 2-Alkylideneoxazolidine-4,5-diones by One-Pot Cyclization of Arylacetonitriles with Heterocumulenes and Ethyl 2-Chloro-2-oxoacetate

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

References

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12

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 (Na₂SO₄), 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: ¹H 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). ¹³C 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 C₁₇H₁₀N₂O₂S: C, 66.65; H, 3.29; N, 9.14. Found: C, 66.85; H, 3.02; N, 8.97.