Cobalt-Containing Mesoporous ZSM-5 Zeolite Catalyzed C=C Bond Cleavage of Alkenes To Form Nitriles

Abstract

Cobalt-containing mesoporous ZSM-5 zeolite (Co-ZSM-5-M) catalyst showed high catalytic activity, selectivity, and excellent reusability in C=C double-bond cleavage of alkenes to form aromatic nitriles. All reactions proceeded smoothly to afford the desired target products in moderate to high yields under the optimal conditions. The Co-ZSM-5-M catalyst was recycled up to at least seven consecutive cycles without significant loss of its catalytic performance.

Key words

mesoporous zeolite - Co-ZSM-5-M - C=C bond cleavage - alkene - nitrile

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• 11 General Procedure for the Preparation of Aromatic Nitriles – Typical Procedure for Compound 2a To the mixture of 1a (190 mg, 1.0 mmol), TMSN₃ (222 mg, 2.5 mmol), NBS, K₃PO₄·3H₂O (251 mg, 2.0 mmol) in MeCN (2.0 mL) was added Co-ZSM-5-M (50 mg) in one portion at r.t. The reaction mixture was heated to 80 °C and stirred for 2 h, until the substrate 1a was consumed as indicated by TLC. The solvent was removed under reduced pressure, and the residue was purified by flash column chromatography (eluent: PE–EtOAc, 30:1) to afford product 2a (99 mg, 86% yield). 4-Methoxybenzonitrile (2a) ¹H NMR (500 MHz, CDCl₃): δ = 7.59 (d, J = 9.0 Hz, 2 H), 6.96 (d, J = 9.0 Hz, 2 H), 3.86 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.8, 133.9, 119.1, 114.7, 103.9, 55.5. 4-Propoxybenzonitrile (2c) ¹H NMR (500 MHz, CDCl₃): δ = 7.56 (d, J = 9.0 Hz, 2 H), 6.94 (d, J = 9.0 Hz, 2 H), 3.96 (t, J = 6.5 Hz, 2 H), 1.89–1.76 (m, 2 H), 1.04 (t, J = 7.5 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.4, 133.9, 119.2, 115.1, 103.6, 69.8, 22.3, 10.3. 4-(Cyclopentyloxy)benzonitrile (2d) ¹H NMR (500 MHz, CDCl₃): δ = 7.56 (d, J = 9.0 Hz, 2 H), 6.91 (d, J = 9.0 Hz, 2 H), 4.84–4.73 (m, 1 H), 1.98–1.88 (m, 2 H), 1.88–1.74 (m, 4 H), 1.70–1.57 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 150.5, 149.9, 146.9, 124.0, 121.6, 64.1, 55.6, 51.2, 34.5.