Clay-Supported Copper Nitrate (Claycop): A Mild Reagent for the Selective Nitration of Aromatic Olefins

Abstract

A straightforward and highly selective method has been developed for the nitration of a wide variety of aromatic and aliphatic olefins by using a clay-supported copper nitrate (Claycop) and a catalytic amount of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, an inexpensive and mild reagent system. High conversions and exclusive E-selectivity, together with the environmentally benign nature of the Claycop reagent, make this a green method and an attractive alternative to established methods.

Key words

nitrations - alkenes

• References

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• 12 Clay-Supported Copper(II) Nitrate (Claycop) K10 clay (30 g) was added to a stirred mixture of Cu(NO₃)₂·3H₂O (26 g) in acetone (400 mL). Stirring was continued for 5–10 min before the solvent was removed in a rotary evaporator at 50 °C. The dry solid crust that adhered to the walls of the flask was scraped off with a spatula, and rotary drying under vacuum was continued for 50 min at 50 °C to give a free-flowing blue powder that showed no loss of reactivity after several months.
• 13 [(E)-2-Nitrovinyl]benzene (2a); Typical Procedure A mixture of styrene (0.104 g, 1.0 mmol), Claycop [0.605 g, 1.5 mmol containing 1.5 equiv Cu(NO₃)₂], TEMPO (0.0156 g, 20 mol%), and 1,4-dioxane (5 mL) was stirred at 80 °C for 1 h. The mixture was then cooled to r.t., and the Claycop was collected by filtration and washed with 1,4-dioxane (3 × 5 mL). The organic phases were combined and concentrated under vacuum. The crude product was purified by recrystallization or column chromatography (EtOAc–hexanes) to give a crystalline yellow solid; yield: 0.1414 g (95%); mp 56–58 °C (Lit.3c 58 °C); ¹H NMR (200 MHz, CDCl₃): δ = 8.03 (d, J = 13.6 Hz, 1 H), 7.53–7.66 (m, 3 H), 7.41–7.53 (m, 3 H); ¹³C NMR (100 MHz, CDCl₃): δ = 139.1, 137.1, 132.1, 130.0, 129.4, 129.1; GC/MS: m/z = 149.1 [M⁺].