Microwave-Assisted Nickel-Catalyzed Synthesis of Benzimidazoles: Ammonia as a Cheap and Nontoxic Nitrogen Source

Fang Ke; Peng Zhang; Yiwen Xu; Xiaoyan Lin; Jin Lin; Chen Lin; Jianhua Xu

doi:10.1055/s-0037-1610843

Synlett, Table of Contents

Synlett 2018; 29(20): 2722-2726
DOI: 10.1055/s-0037-1610843

letter

Microwave-Assisted Nickel-Catalyzed Synthesis of Benzimidazoles: Ammonia as a Cheap and Nontoxic Nitrogen Source

Fang Ke ◊*

College of Pharmacy, Fujian Medical University, Fuzhou 350004, P. R. of China Email: kefang@mail.fjmu.edu.cn

,

Peng Zhang ◊

,

Yiwen Xu

,

Xiaoyan Lin

,

Jin Lin

,

Chen Lin

,

Jianhua Xu

› Author Affiliations

Abstract

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◊ These authors contributed equally to this work.

Abstract

An efficient and convenient Ni-catalyzed C–N bond formation for the synthesis of various benzimidazoles from various 2-haloanilines, aldehydes, and ammonia in a concise manner is reported. This protocol uses commercially available, nonhazardous, clean ammonia as a reaction partner instead of other nitrogen sources. Benzimidazoles, as the sole products, were obtained in high to excellent yields (up to 95%).

Key words

nickel catalysis - C–N bond formation - benzimidazoles - microwave heating - ammonia

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References

References and Notes

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12 Benzimidazoles 2a–w; General Procedure A 10 mL glass tube was charged with the appropriate 2-haloaniline (0.5 mmol), 25–28% aq NH₃ (2 mL), the appropriate aldehyde (0.6 mmol), NiCl₂ (11.88 mg, 0.05 mmol), quinolin-8-ol (7.258 mg, 0.05 mmol), and Cs₂CO₃ (325.82 mg, 1.0 mmol). The vessel was then sealed with a septum and placed in the cavity of a Discover microwave synthesizer (CEM Corp., Buckingham, UK), and irradiated at 130 W. The temperature was ramped from r.t. to the desired temperature of 100 °C, then held at this temperature for 13 min. The mixture was stirred continuously during the reaction. The mixture was then allowed to cool to r.t. and the solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel) to afford the corresponding product. The structures of the products were confirmed by NMR and MS spectroscopic analyses. 2-Phenyl-1H-benzo[d]imidazole (2a) Light-yellow solid; yield: 89.24 mg (92%). ¹H NMR (400 MHz, MeCN-d ₃): δ = 7.26–7.28 (m, 2 H), 7.55–7.64 (m, 5 H), 8.13 (d, J = 4.0 Hz, 2 H), 10.96 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 151.70, 144.29, 135.48, 130.65, 130.30, 129.42, 126.91, 123.00, 122.14, 119.35, 111.79. ESI-MS: m/z = 195.1 [M + H]⁺.

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