Cobalt nitride enabled benzimidazoles production from furyl/aryl bio-alcohols and <i>o</i>-nitroanilines without an external H-source

doi:10.1007/s11705-022-2174-y

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (1) : 68-81 https://doi.org/10.1007/s11705-022-2174-y

RESEARCH ARTICLE

Cobalt nitride enabled benzimidazoles production from furyl/aryl bio-alcohols and o-nitroanilines without an external H-source

Chuanhui Li, Li-Long Zhang, Hu Li(

), Song Yang(

)

State Key Laboratory Breeding Base of Green Pesticide & Agricultural Bioengineering, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, Guiyang 550025, China

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Abstract

Benzimidazole derivatives have wide-spectrum biological activities and pharmacological effects, but remain challenging to be produced from biomass feedstocks. Here, we report a green hydrogen transfer strategy for the efficient one-pot production of benzimidazoles from a wide range of bio-alcohols and o-nitroanilines enabled by cobalt nitride species on hierarchically porous and recyclable nitrogen-doped carbon catalysts (Co/CN_x-T, T denotes the pyrolysis temperature) without using an external hydrogen source and base additive. Among the tested catalysts, Co/CN_x-700 exhibited superior catalytic performance, furnishing 2-substituted benzimidazoles in 65%–92% yields. Detailed mechanistic studies manifest that the coordination between Co²⁺ and N with appropriate electronic state on the porous nitrogen-doped carbon having structural defects, as well as the remarkable synergetic effect of Co/N dual sites contribute to the pronounced activity of Co/CN_x-700, while too high pyrolysis temperature may cause the breakage of the catalyst Co–N bond to lower down its activity. Also, it is revealed that the initial dehydrogenation of bio-alcohol and the subsequent cyclodehydrogenation are closely correlated with the hydrogenation of nitro groups. The catalytic hydrogen transfer-coupling protocol opens a new avenue for the synthesis of N-heterocyclic compounds from biomass.

Keywords biomass conversion furanic compounds benzimidazoles hydrogen transfer bifunctional catalysis

Corresponding Author(s): Hu Li,Song Yang

About author:

Changjian Wang and Zhiying Yang contributed equally to this work.

Online First Date: 28 July 2022 Issue Date: 21 February 2023

Cite this article:

Chuanhui Li,Li-Long Zhang,Hu Li, et al. Cobalt nitride enabled benzimidazoles production from furyl/aryl bio-alcohols and o-nitroanilines without an external H-source[J]. Front. Chem. Sci. Eng., 2023, 17(1): 68-81.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2174-y
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I1/68

Fig.1 Schematic illustration of furyl/aryl bio-alcohols evolved from lignocellulose biomass.

Fig.2 Synthetic routes to the synthesis of benzimidazoles: (a) conventional approach, (b) dehydrogenation coupling, (c) hydrogen transfer strategy, and (d) this work.

Fig.3 Schematic for preparation of Co/CN_x-T catalysts from (a) ZIF-67, (b) scanning electron microscopy (SEM) image, (c) transmission electron microscope (TEM) image, (d) high resolution TEM (HRTEM) image, (e) scanning transmission electron microscopy-high angle annular dark field image (HTEM-HAADF), and (f–j) elemental mappings of Co/CN_x-700: (g) Co element, (h) N element, (i) C element and (j) O element.

Fig.4 (a) XRD patterns, (b) Raman spectra, (c) N₂ adsorption–desorption isotherms, and (d) Barrett–Joyner–Halenda pore size distribution of Co/CN_x-T catalysts.

Fig.5 The high-resolution XPS spectra of (a) Co 2p, (b) N 1s, (c) C 1s, and (d) O 1s of Co/CN_x-T.

Tab.1 Synthesis of benzimidazoles from o-nitroaniline (1a) and benzyl alcohol (2a) over Co/CN_x-T ^a)

Fig.6 (a) Catalytic activity of Co/CN_x calcined at different temperatures (600–800 ºC) plotted with the surface proportion of Co−N_x active sites, and (b) catalytic activity of Co/CN_x calcined at different temperatures (600–800 ºC) plotted with its specific surface area.

Fig.7 Control experiments to explore the hydrogen transfer mechanism: (a) reaction of 5a with 2a to form 3a, (b) reaction of 1a with 6a to form 3a and (c) reaction of 5a with 6a to form 3a under the same reaction conditions.

Fig.8 Computed free energy profiles for dehydrogenation of benzyl alcohol on Co⁰(111) or CoN₄ catalyst (TS: transition state; IM: intermediate).

Fig.9 Recyclability of Co/CN_x-700 in the synthesis of 3a from 1a and 2a (Purple: Co/CN_x-700 was treated by N₂ flow at 700 °C for 1 h after each cycle. Olive: there is no other treatment after each cycle of Co/CN_x-700).

Fig.10 (a) N₂ adsorption–desorption isotherms; (b) thermogravimetric curves; (c) XRD patterns of Co/CN_x-700 and Co/CN_x-700(ac)²; (d) HRTEM image of Co/CN_x-700(ac)².

Fig.11 Synthesis of benzimidazoles from alcohols and o-nitroanilines (reaction conditions: o-nitroanilines (0.5 mmol), alcohols (1.5 mmol), Co/CN_x-700 (30 mg, 1.67 mol % of Co), cyclohexane (2 mL) at 150 °С for 10 h).

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