Efficient Heterogeneous Palladium-Montmorillonite Catalysts for Heck Coupling of Aryl Bromides and Chlorides

 

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Abstract

New palladium catalysts were prepared using ion exchange or intercalation of Pd species into montmorillonite. The catalysts promote Heck reaction of various aromatic halides including aryl chlorides to give coupling products in high yields at low catalyst ratios down to 0.001 mol%.

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Preparation of Catalysts. Before catalyst synthesis Na-montmorillonite (Bentolite H, Laporte) was suspended in distilled water overnight with stirring at r.t.
Pd-montm1 (2.16% Pd loading): Pd(NO₃)₂·3H₂O (0.4 g) dissolved in water and acidified with concd HNO₃ (0.4 mL) was added to Na-montmorillonite (8 g). After stirring for 4 h the solid was separated by centrifugation and washed thoroughly with water.
Pd-montm2 (1.29% loading): Pd(NO₃)₂·3H₂O (0.33 g) dissolved in water was added to Na-montmorillonite (5 g). After stirring for 4 h the solid was separated by centrifugation and washed thoroughly with water. Finally, the wet products were oven-dried (95 °C, 1 Torr, 6 h). The palladium content was determined by means of inductively coupled plasma atomic emission spectroscopy (ICP-AES). Catalysts used in recycling experiments were reduced in flowing hydrogen (200 °C, 2 h).

General Procedure for Heck Coupling: Reactions were carried out in 5 mL or 25 mL glass vials equipped with a Teflon screw cap with magnetic stirring using aryl halide (0.5-10 mmol) in NMP solvent. No special precaution was taken to exclude air or moisture. Reaction conditions (reactant and catalyst ratios, reaction time and temperature) are given in tables. Toluene or biphenyl was used as internal standard to calculate conversions and yields. All products are known compounds and were identified by GC-MS (HP 5890 GC +HP 5970 mass selective detector) and ¹H NMR (Bruker Avance DRX 500).

Catalyst Recycling: Bromobenzene (1 mmol), styrene (1.5 mmol), Na₂CO₃ [1.2 mmol or Et₃N (1 mmol)-Na₂CO₃ (0.5 mmol)], and Pd catalyst (0.3 mol%) were reacted in NMP (2 mL). Catalyst samples after reaction were separated by centrifugation, washed successively with acetone, water, acetone and, finally, dried under an infra lamp and reused.