Covalently Bonded Ionic Liquid-Type Sulfamic Acid onto SBA-15: SBA-15/NHSO₃H as a Highly Active, Reusable, and Selective Green Catalyst for Solvent-Free Synthesis of Polyhydroquinolines and Dihydropyridines

Abstract

Amine-functionalized ordered mesoporous organic–inorganic hybrid materials are designed as solid supports to covalently immobilize the SO₃H group to achieve sulfamic acid (SBA-15/ NHSO₃H) as a novel catalyst. SBA-15/NHSO₃H as ionic liquid-type heterogeneous catalyst could be separated easily from reaction products and recycled, showing superiority over homogeneous catalysts.

Keywords

SBA-15/NHSO₃H - supported sulfamic acid - multicomponent reaction - mesoporous solid

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• 10 General Procedure for the Synthesis of Polyhydroquinolines and Dihydropyridines A mixture of aldehyde (1 mmol), β-dicarbonyl compound (1 or 2 mmol), NH₄OAc (2.5 mmol), dimedone (1 mmol, when used), and SBA-15/NHSO₃H (5 mol%) was stirred at 55 °C. After complete disappearance of starting material as indicated by TLC, the resulting mixture was diluted with hot EtOAc (10 mL) and filtered. The catalyst was completely recovered from the residue. Representative Spectroscopic Data
  Methyl 2,7,7-Trimethyl-5-oxo 4-Phenyl-1,4,5,6,7,8-hexahydro-3-quinolinecarboxylate (4a) ¹H NMR (300.13 MHz, CDCl₃): δ = 0.94 (s, 3 H), 1.09 (s, 3 H), 2.11–2.40 (m, 8 H), 3.62 (s, 3 H), 5.08 (s, 1 H), 7.08–7.31 (m, 5 H). Diethyl 2,6-Dimethyl-4-phenyl-1,4-dihydropyridine-3,5-dicarboxylate (5a) IR (KBr): 3342, 1700, 1657, 1473, 1198, 1129 cm^–1. ¹H NMR (300.13 MHz, CDCl₃): δ = 1.23 (t, ³ J _HH = 7.0 Hz, 6 H), 2.34 (s, 6 H), 4.12 (q, ³ J _HH = 7.0 Hz, 4 H), 4.91 (s, 1 H), 5.68 (s, 1 H), 7.07–7.43 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 14.91, 19.56, 39.43, 59.82, 103.14, 127.25, 127.32, 128.34, 129.61, 146.19, 148.25, 167.34.