A Facile and Efficient Synthesis of New Polysubstituted Indeno[1,2-b]pyri­dines via One-Pot, Three-Component Microwave-Assisted Reaction

Abstract

A rapid and efficient method is developed to synthesize new polysubstituted indeno[1,2-b]pyridines via three-component microwave-assisted reaction of arylidenemalononitrile, 1,3-indane­dione and aromatic amine. This method has the advantages of short synthetic route, operational simplicity, increased safety for small-scale high-speed synthesis, and minimal environmental impact.

Key words

arylidenemalononitrile - indenopyridine derivatives - multicomponent - heterocycles - amines

References and Notes

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20

Typical Procedure: Preparation of Compounds 5, 7 and 10.
The reactions were performed in a monomodal Emrys^TM Creator from Personal Chemistry, Uppsala, Sweden. In an Emrys^TM reaction vial (10 mL), arylidenemalononitrile (2, 1 mmol), 1,3-indenodione (3, 1 mmol) or dimedone (8, 1 mmol), aromatic amine (4, 1.2 mmol) or aliphatic amine (6, 1.2 mmol) and DMF (1.0 mL) were mixed and then capped. The mixture was irradiated for 4-9 min at 120 °C under microwave irradiation (initial power 100 W and maximum power 200 W). Upon completion of the reaction as monitored by TLC, the reaction mixture was cooled to r.t. and then poured into cold H₂O. The solid product was filtered, washed with H₂O and EtOH (95%). The solid was purified by recrystallization from EtOH (95%). Spectral data and elemental analyses of selected compounds are given here.
Compound 5g: IR (KBr): ν = 3301, 2208, 1711, 1606, 1559, 1497, 1387, 1329, 753, 704 cm^-1. ¹H NMR (DMSO-d ₆): δ = 9.92 (s, 1 H, NH), 7.95 (d, 1 H, J = 4.8 Hz, thiophenyl-H), 7.71 (t, 4 H, J = 7.6 Hz, ArH), 7.65-7.58 (m, 3 H, ArH), 7.44 (t, 2 H, J = 8.0 Hz, ArH), 7.29 (t, 1 H, J = 4.4 Hz, thiophenyl-H), 7.23-7.20 (m, 1 H, thiophenyl-H) ppm. Anal. Calcd for C₂₃H₁₃N₃OS: C, 72.80; H, 3.45; N, 11.07; S, 8.45. Found: C, 72.97; H, 3.34; N, 11.21; S, 8.34.
Compound 5k: IR (KBr): ν = 3306, 2213, 1713, 1610, 1571, 1520, 1240, 1009, 813, 763 cm^-1. ¹H NMR (DMSO-d ₆): δ = 9.90 (s, 1 H, NH), 7.76 (d, 2 H, J = 8.4 Hz, ArH), 7.70-7.68 (m, 2 H, ArH), 7.61-7.60 (m, 2 H, ArH), 7.58 (d, 2 H, J = 8.4 Hz, ArH), 7.53 (d, 2 H, J = 8.4 Hz, ArH), 7.24 (d, 2 H, J = 8.4 Hz, ArH), 2.35 (s, 3 H, CH₃) ppm. Anal. Calcd for C₂₆H₁₆BrN₃O: C, 66.97; H, 3.46; N, 9.01. Found: C, 66.89; H, 3.54; N, 9.17.
Compound 7a: IR (KBr): ν = 3437, 3335, 2218, 1702, 1621, 1572, 1355, 1201, 1007, 749; 656 cm^-1. ¹H NMR (DMSO-d ₆): δ = 7.74 (d, 2 H, J = 8.4 Hz, ArH), 7.67-7.65 (m, 2 H, ArH), 7.58-7.56 (m, 2 H, ArH), 7.57 (d, 2 H, J = 8.4 Hz, ArH), 5.46 (s, 2 H, NH₂), 4.98 (s, 1 H, CH) ppm. Anal. Calcd for C₁₉H₁₁BrN₂O₂: C, 60.18; H, 2.92; N, 7.39. Found: C, 60.35; H, 2.74; N, 7.25.