Hydroarylation of Styrenes with Electron-Rich Arenes Over Acidic Ion-Exchange Resins

Abstract

A series of acidic cation-exchange resins were used for the hydroarylation of resorcinol with styrene, in which resin D072 exhibited the excellent catalytic performance in this reaction with 99% conversion of styrene and 90% selectivity of 4-(1-phenylethyl)resorcinol. It was applied to the hydroarylation of various electron-rich arenes with styrenes, and the hydroarylated products were quantitatively obtained. This catalyst could be used for four consecutive runs with slight decrease in activity. The hydroarylation of resorcinol with styrene over resin D072 in a fixed bed was completed effectively with 94% selectivity and 99% conversion, and this green continuous process is potentially applicable to large-scale productions.

GRAPHICAL ABSTRACT

Keywords:

• Acidic cation-exchange resin
• fixed-bed reactor
• Friedel–Crafts hydroarylation
• green chemistry
• heterogeneous catalyst

Notes

^a Reaction condition: 15 mmol of resorcinol, 5 mmol of styrene, 30 wt% (based on styrene) of catalyst, reflux in DCE for 4 h.

^b HPLC conversion of styrene.

^c HPLC yield of the product.

^d Single/double substituted isomers were determined by ¹H NMR and ¹³C NMR.

^a Reaction conditions: 15 mmol arene, 5 mmol (substituted) styrene, 30 wt% D072, reflux in DCE, 4 h.

^b Main product.

^c HPLC conversion of styrene.

^d HPLC yield of products.

^e Main product: other isomers.

^f The selectivity was detected by ¹H NMR.

^a Reaction conditions: 15 mmol arene, 5 mmol (substituted) styrene, 30 wt% D072, reflux in DCE for 4 h.

^b Main product.

^c HPLC conversion of styrene.

^d HPLC yield of products.

^e Main product : other isomers.

^a Reaction condition: 15 mmol of resorcinol, 5 mmol of styrene, 30 wt% (based on styrene) of catalyst, reflux in DCE for 4 h.

^b HPLC conversion of styrene.

^c HPLC yields of product.

^d Single/double substituted isomer were determined by ¹H NMR and ¹³C NMR.

^a Reaction conditions: flow rate 0.3 mL/min, temperature 72 °C.

^b HPLC conversion of styrene.

^c HPLC yields of product 1.

^d Single/double substituted isomer were determined by ¹H NMR and ¹³C NMR.

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