An atom-efficient electrosynthesis strategy for organic halides

doi:10.1016/S1872-2067(25)64796-6

Abstract

Abstract:

Existing organic halide synthesis routes typically employ elemental halogens (X₂, X = Cl or Br), leading to low atom economy and significant environmental pollution. In this work, we developed an atom efficient electrosynthesis and separation strategy for halogenation reagents — N-chlorosuccinimide (NCS) and N-bromosuccinimide (NBS) — at high current densities. Faradic efficiency (FE) of 91.0% and 81.3% was achieved for NCS and NBS generation on RuO_x/TiO₂/Ti in a batch cell, respectively. Electrosynthesis of NCS likely involves both heterogeneous catalytic and homogeneous tandem pathways, while NBS is likely formed in a Langmuir-Hinshelwood mechanism with a proton-coupled electron transfer as the rate-determining step. A coupled continuous electrocatalytic synthesis and in situ separation setup was developed for the efficient production of NCS and NBS, which yielded 0.77 g of NCS in 12000 s and 0.81 g of NBS in 15000 s, both with relative purity exceeding 95%. The halogenation of acetone using NCS and NBS enabled gram-scale production of the key intermediate in organic synthesis, 1-halogenacetone, with over 95% recovery of succinimide.

Key words: Electrocatalysis, Process intensification, Halogenation reaction, Organic halides synthesis, N-chlorosuccinimide, N-bromosuccinimide

Yiwei Liu, Xiaoxia Chang, Bingjun Xu. An atom-efficient electrosynthesis strategy for organic halides[J]. Chinese Journal of Catalysis, 2025, 78: 170-181.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64796-6

https://www.cjcatal.com/EN/Y2025/V78/I11/170

Figures/Tables 6

Fig. 1. (a) XRD profiles of synthesized RuOx/TiO2/Ti and IrOy/TiO2/Ti. (b) XPS spectra of synthesized RuOx/TiO2/Ti and IrOy/TiO2/Ti. SEM images with elemental mapping of synthesized RuOx/TiO2/Ti (c) and IrOy/TiO2/Ti (d).

Fig. 2. (a) Reaction scheme of electrosynthesis of NCS and NBS (X = Cl, Br). Impact of reaction conditions on FE and current density in electrocatalytic synthesis of NCS (b,d) and NBS (c,e). Effect of the applied potential in NCS (b) and NBS (c) synthesis. Effect of pH in NCS (d) and NBS (e) synthesis. In (d) and (e), H2SO4 (aq), KH2PO4 (aq), K2SO4 (aq), H3BO3-KB(OH)4 (aq) and KOH (aq) were used for regulating pH from 1 to 13.

Fig. 3. Impact of reaction conditions on FE and current density in electrocatalytic synthesis of NCS (a,b) and NBS (c,d). Effect of the C(KX) (X = Cl or Br) in NCS (a) and NBS (c) synthesis. Effect of m(succinimide) in NCS (b) and NBS (d) synthesis. Synthesis of NCS and NBS was carried out at 1.2 and 1.0 V, respectively, at pH = 7.

Fig. 4. CVs curves under different m(succinimide) in NCS (a) and NBS (c) synthesis. CVs curves under different C(KX) in NCS (b, X = Cl) and NBS (d, X = Br) synthesis. Scanning rate: 50 mV/s. The anode solution was prepared by 16 mL 0.1 mol/L K2SO4.

Fig. 5. (a) Schematic diagram of the experimental setup. (b) Continuous synthesis and in-situ separation of NCS under constant 120 mA electrolysis. Geometric area of anode: 0.9 cm2. Liquid flow rate: 40 mL/min. The added feedstock aqueous contained 3 mol/L KCl and 0.75 g/10 mL succinimide. (c) Continuous synthesis and in-situ separation of NBS under constant 100 mA electrolysis. Geometric area of anode: 0.9 cm2. Liquid flow rate: 40 mL/min. The added feedstock aqueous contained 1 mol/L KBr. The anode and reference electrode in the continuous reactor are 2 cm apart, while the separation is 0.2 cm in the batch cell. Thus, the internal IR correction was conducted in the continuous reactor. IR-uncorrected data are included in Fig. S12(b), (c). The anolyte was maintained at room temperature during the electrolysis process.

Fig. 6. (a) Performance in halogenation reaction of acetone with NCS and NBS. (b) Existing and electrocatalysis-coupled routes for halogenated acetone.

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