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Synlett 2018; 29(20): 2722-2726
DOI: 10.1055/s-0037-1610843
DOI: 10.1055/s-0037-1610843
letter
Microwave-Assisted Nickel-Catalyzed Synthesis of Benzimidazoles: Ammonia as a Cheap and Nontoxic Nitrogen Source
This project was sponsored by Research Fund of Fujian Provincial Foundation (2016J01686, 2016J01372, 2016Y9051, 2017J01820, 2017J01820).Further Information
Publication History
Received: 05 September 2018
Accepted after revision: 23 October 2018
Publication Date:
23 November 2018 (online)
◊ 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%).
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610843.
- Supporting Information
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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]+.