l-Proline-Catalysed Unusual Product Formation from the Reaction of 4- Hydroxydithiocoumarin and Aldehydes through a Pseudo-Three-Component Reaction

Abstract

A convenient and highly efficient synthetic protocol is reported for the synthesis of hitherto unreported thiopyrano{2,3-b:6,5-b′}bis(thiochromene)-12,14(13H)-diones by a domino pseudo-three-component reaction utilizing 4-hydroxydithiocoumarin and aldehydes. Single-crystal X-ray crystallographic analysis of the 13-phenyl-12H-thiopyrano[2,3-b:6,5-b′]bis(thiochromene)-12,14(13H)- dione derivative shows a layered structure that is stabilized by the unexpected C–S···π interactions.

Key words

multicomponent reaction - l-proline - 4-hydroxydithiocoumarin - thiopyrano[2,3-b:6,5-b′]bis(thio chromene)-12,14(13H)-dione

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• 15 A mixture of 4-hydroxydithiocoumarin (2 mmol), benzaldehyde (1 mmol), and l-proline (0.012 mg, 10 mol%) was dissolved in MeCN (2 mL) into an oven-dried 25 mL round-bottomed flask and heated to reflux with stirring, progress of reaction being monitored by TLC. The precipitate was filtered off and washed with MeCN to furnish the pure product 3a. Yield 85%, white solid, mp 306–307 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.03 (s, 1 H), 7.12–13 (m, 1 H), 7.16–7.19 (m, 2 H), 7.45 (d, J = 7.8 Hz, 2 H), 7.49–7.53 (m, 4 H), 7.57–7.59 (m, 2 H), 8.53 (d, J = 8.4 Hz, 2 H). ¹³C NMR (150 MHz, CDCl₃): δ = 39.7, 125.6, 127.3, 128.2, 128.3, 128.6, 130.1, 131.0, 131.9, 132.5, 135.7, 139.8, 142.3, 176.3. IR (KBr): ν_max = 1146, 1155, 1233, 1277, 1325, 1340, 1435, 1454, 1491, 1547, 1572, 1588, 1616, 2848, 2925, 3059 cm^–1. Anal. Calcd for C₂₅H₁₄O₂S₃: C, 67.85; H, 3.19. Found: C, 67.73; H, 3.10.