Synthesis of Aryl Nitriles via Aerobic Oxidative Cleavage of Aryl C=C Bonds with (NH₄)₂CO₃ as the Nitrogen Source

Abstract

An aerobic oxidative method was developed for conversion of arylethenes to aromatic nitriles using (NH₄)₂CO₃ as the nitrogen source and Cu(NO₃)₂ as the catalyst. The present method allowed a series of arylethenes to underwent oxidative cleavage of C=C bonds to give the targeted products in low to high yields. In addition, the present conditions are compatible with many groups such as alkyl, alkoxy, N,N-dimethylamino, chloro, bromo, iodo, ester, cyano group, and so on.

Key words

aromatic nitriles - arylethenes - carbon–carbon double bonds - oxidative cleavage - oxygen

• References and Notes

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• 18 Representative Procedure for Conversion of Various Arylethenes to Aromatic Nitriles To a stainless steel autoclave lined with Teflon, 0.5 mmol substrate, 0.075 mmol Cu(NO₃)₂, 1 mmol (NH₄)₂CO₃, and 2 mL DMSO were added. Then the reactor was filled with 2 MPa oxygen and was heated under magnetic stirring at 140 °C for 30 h or 40 h (Caution: the use of the high-pressure oxygen is potentially hazardous. Thus, experiments using the high-pressure oxygen must only be carried out under rigorous safety precautions, and it is required to use the appropriate high-pressure reactor to avoid the potential leakage or explosion of the gas). Once the reaction time was reached, the mixture was cooled to room temperature, diluted with 30 mL diethyl ether, and filtered via a Celite pad. The organic mixture was washed with water (3 × 5 mL), dried with anhydrous sodium sulfate, and concentrated in vacuum. GC analysis provided the GC yields of the product with an internal standard. In addition, the combined crude product from another 1–5 parallel experiments was purified by column chromatography and identified by ¹H NMR and ¹³C NMR spectroscopy. All the products are the known compounds, and the analytical data of several typical compounds are as follows: 4-Methoxylbenzonitrile2k ¹H NMR (400 MHz, CDCl₃): δ = 7.59 (d, J = 8.9 Hz, 2 H), 6.95 (d, J = 8.9 Hz, 2 H), 3.86 (s, 3 H) ppm. ¹³C NMR (101MHz, CDCl₃): δ = 162.9, 134.0, 119.2, 114.8, 104.0, 55.6 ppm. 4-Phenylbenzonitrile2k ¹H NMR (400 MHz, CDCl₃): δ = 7.72 (d, J = 8.4 Hz, 2 H), 7.68 (d, J = 8.3 Hz, 2 H), 7.59 (d, J = 7.7 Hz, 2 H), 7.48 (t, J = 7.5 Hz, 2 H), 7.45–7.38 (m, 1 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 145.7, 139.2, 132.6, 129.1, 128.7, 127.8, 127.3, 118.97, 110.9 ppm. 1-Naphthonitrile2k ¹H NMR (400 MHz, CDCl₃): δ = 8.22 (d, J = 8.3 Hz, 1 H), 8.06 (d, J = 8.3 Hz, 1 H), 7.89 (t, J = 7.5 Hz, 2 H), 7.67 (t, J = 7.6 Hz, 1 H), 7.60 (dd, J ₁ = 7.9, J ₁ = 7.1 Hz, 1 H), 7.50 (t, J = 7.7 Hz, 1 H) ppm. ¹³C NMR (101 MHz, CDCl₃): δ = 133.3, 132.9, 132.6, 132.4, 128.7, 128.6, 127.6, 125.1, 125.0, 117.9, 110.2 ppm.
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