Dehydrative Amination of Alcohols in Water Using a Water-Soluble Calix[4]resorcinarene Sulfonic Acid

Abstract

A protocol for the dehydrative amination of alcohols in water using a water-soluble calix[4]resorcinarene sulfonic acid as a reusable multifunctional catalyst was developed.

aminations - calixarenes - green chemistry - host-guest systems - phase-transfer catalysis

References and Notes

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<A NAME="RY00108ST-19">19</A>

General Experimental Procedure for Dehydrative Amination in H ₂ O (Table 2): Alcohol (0.30 mmol) and p-toluenesulfonamide (0.45 mmol) were added to a solution of water-soluble calix[4]resorcinarene sulfonic acid 1 ^13,20 (0.030 mmol) in H₂O (1 mL) with stirring, and the reaction mixture was vigorously stirred at 60 °C for an additional 24 h. After the addition of sat. aq NaHCO₃ solution (3 mL), the resulting mixture was extracted with EtOAc (3 × 3 mL). The combined extracts were dried over anhyd Na₂SO₄ and evaporated. The products were purified by flash chromatography on silica gel to yield the amination product.
Recycling Experiments (Table 3): Alcohol (0.90 mmol) and p-toluenesulfonamide (1.08 mmol) were added to a solution of water-soluble calix[4]resorcinarene sulfonic acid 1 (0.090 mmol) in H₂O (3 mL) with stirring, and the reaction mixture was vigorously stirred at 60 °C for an additional 24 h. After each reaction, EtOAc (3 mL) was added to the reaction mixture, and the solution was stirred for 5 min. The resulting mixture was allowed to stand for 5 min and then the organic phase was removed via a syringe. This extraction procedure was repeated twice. The remaining aqueous catalyst solution was reused directly in the next cycle. Isolation of the amination product 2a was performed in a manner similar to that described above.

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