Efficient electrosynthesis method of deuterated acetic acid and deuterated acetyl compounds with D2O as deuterium source

Abstract

The invention discloses a deuterated acetic acid and deuterated acetyl compound high-efficiency electrosynthesis method taking D2O as a deuterium source, and the deuterated acetic acid high-efficiency electrosynthesis method comprises the following steps: in a standard three-electrode double-chamber electrolysis system, taking deuterium water as the deuterium source, adding an electrolyte and a surfactant, and reducing trichloroacetic acid through a constant current electrolysis method to obtain deuterated acetic acid; wherein the monometal electrode for in-situ growth of the nanorod is a working electrode in the standard three electrodes. The method is high in conversion rate and selectivity, is an efficient synthesis method, takes cheap deuterium water as a deuterium source, is mild in reaction condition, does not need high temperature and high pressure, is simple to operate, is easy to separate a product, and can be used repeatedly, and a green, safe and efficient method is provided for synthesis of deuterated acetyl drugs.

Description

Technical Field

[0001] This invention relates to the field of electrosynthesis technology of deuterated acetic acid and its pharmaceuticals, and particularly to an efficient electrosynthesis method for deuterated acetic acid and deuterated acetyl compounds using D2O as the deuterium source. Background Technology

[0002] Deuteration, as an important labeling tool, has wide applications in medicinal chemistry, labeling and tracing, and reaction mechanism research. Drug deuteration is a commonly used method to alter the absorption, distribution, metabolism, and excretion (ADME) processes of drug molecules. Deuteration at key sites of drug metabolism can significantly improve drug stability and prolong the drug's half-life. Acetyl compounds are important building blocks for small molecule drugs; deuteration modification of acetyl drugs, such as acetaminophen, oseltamivir, and aspirin, can effectively improve their metabolic stability and biological activity, further enhancing their pharmacological properties and value. The most common method for synthesizing acyl compounds is the acylation of carboxylic acid compounds.

[0003] Existing technology (invention patent application number CN202210216341.7) discloses a process for producing deuterated acetic acid, which involves adding acetic anhydride and a suitable catalyst to a flask, adding heavy water in batches under oil bath and magnetic stirring conditions at 60°C, and carrying out the reaction under argon protection. After the reaction, the product is collected and distilled to obtain deuterated acetic acid. However, the traditional method of preparing acetic acid by hydrolysis of acetic anhydride cannot effectively achieve the deuteration of acetic acid. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide an efficient electrosynthesis method for deuterated acetic acid and deuterated acetyl compounds using D2O as the deuterium source.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] A first aspect of the present invention provides a method for the efficient electrosynthesis of deuterated acetic acid using D2O as a deuterium source, comprising the following steps:

[0007] In a standard three-electrode two-chamber electrolysis system, deuterated water is used as the deuterium source, and electrolytes and surfactants are added. Trichloroacetic acid is reduced to deuterated acetic acid by constant current electrolysis.

[0008] Among them, the single metal electrode of the in-situ grown nanorod is the working electrode in the standard three-electrode system.

[0009] Furthermore, the standard three-electrode two-chamber electrolysis system includes:

[0010] The working electrode was a copper metal electrode with in-situ grown nanorods, the reference electrode was Hg / HgO, and the counter electrode was a Pt sheet.

[0011] The H-type dual-chamber standard three-electrode electrolytic cell is the container, with the cathode electrolytic chamber and the anode electrolytic chamber separated by a proton exchange membrane.

[0012] Further, the step of adding electrolyte and surfactant to reduce trichloroacetic acid to deuterated acetic acid via constant current electrolysis includes:

[0013] Add the reaction substrate, electrolyte, surfactant, and deuterium water to the cathode electrolysis chamber, and add the electrolyte and deuterium water to the anolyte electrolysis chamber;

[0014] A reaction solution containing deuterated acetic acid was prepared by constant current electrolysis.

[0015] The reaction solution was distilled to obtain the product deuterated acetic acid.

[0016] Furthermore, the electrolyte is an alkali and / or an alkali salt;

[0017] The surfactant is n-octyltrimethylammonium bromide.

[0018] A second aspect of the present invention provides an efficient electrosynthesis method for deuterated acetyl compounds using D2O as a deuterium source, comprising the following steps:

[0019] Deuterated acetic acid is obtained by performing the efficient electrosynthesis method of deuterated acetic acid with D2O as the deuterium source as described in the first aspect;

[0020] Deuterated acetyl compounds were synthesized using deuterated acetic acid.

[0021] Furthermore, the deuterated acetyl compounds include deuterated aspirin, deuterated acetaminophen, deuterated celecoxib, and deuterated oseltamivir.

[0022] A third aspect of the present invention provides a working electrode for use in the efficient electrosynthesis method of deuterated acetic acid with D2O as a deuterium source as described in the first aspect, or for use in the efficient electrosynthesis method of deuterated acetyl compounds with D2O as a deuterium source as described in any one of the second aspects, wherein the working electrode comprises copper foam and copper nanorods grown in situ on the copper foam.

[0023] Furthermore, the working electrode is a CuNRs working electrode.

[0024] Furthermore, the fabrication steps of the CuNRs working electrode include:

[0025] Copper foam pretreatment;

[0026] The pretreated copper foam was placed in a beaker containing a mixed solution of sodium hydroxide and ammonium persulfate, cooled in an ice-water bath for 2-4 hours, rinsed with ethanol and deionized water, and dried to obtain Cu(OH)2NRs.

[0027] The obtained Cu(OH)2NRs material was calcined at 60℃ for 2 hours in an argon atmosphere, then calcined at 120℃ for 4 hours, and finally calcined at 180℃ for 6 hours. After cooling to room temperature, it was washed with ethanol and deionized water and dried to obtain CuO NRs.

[0028] The obtained CuO NRs were used as the intermediate working electrode, Hg / HgO as the reference electrode, and a carbon rod as the counter electrode. A current of -50mA was applied in an H-type electrolytic cell, and the electrolyte was a 0.5M K2CO3 solution. Electrolysis was carried out for 10 to 30 minutes to obtain the Cu NRs working electrode.

[0029] Furthermore, the copper foam pretreatment includes:

[0030] The copper foam was immersed in acetone and ultrasonically cleaned to remove organic matter from the surface.

[0031] The foamed copper, from which surface organic matter has been removed, is placed in an acid solution for ultrasonic cleaning to remove surface oxides.

[0032] The copper foam with surface oxides removed is ultrasonically cleaned in deionized water to remove acetone and acid from the surface.

[0033] The beneficial effects of this invention are:

[0034] In an exemplary embodiment of the present invention, the conversion rate and selectivity are high, making it a highly efficient synthetic method. Furthermore, the present invention uses inexpensive deuterium water as the deuterium source, employs mild reaction conditions, eliminates the need for high temperature and high pressure, simplifies operation, facilitates product separation, and allows for catalyst reuse. This provides a green, safe, and efficient method for the synthesis of deuterated acetyl drugs, effectively avoiding the problems of other synthetic methods, such as the use of precious metal catalysts, expensive deuterium gas and deuterated organic reagents, complex operation, long reaction time, and low deuteration rate. Attached Figure Description

[0035] Figure 1 This is a schematic diagram illustrating the principle of a highly efficient electrosynthesis method for deuterated acetic acid using D2O as a deuterium source, provided in an exemplary embodiment of the present invention.

[0036] Figure 2 This is a performance comparison chart of using different surfactants for the preparation of deuterated acetic acid in an exemplary embodiment of the present invention;

[0037] Figure 3 The deuterated acetic acid product prepared in an exemplary embodiment of the present invention is... 13 C NMR spectrum;

[0038] Figure 4 The NMR spectrum of the deuterated aspirin product prepared in an exemplary embodiment of the present invention is shown below.

[0039] Figure 5 The NMR spectrum of the deuterated acetaminophen product prepared in an exemplary embodiment of the present invention is shown below.

[0040] Figure 6 The NMR spectrum of the deuterated celecoxib product prepared in an exemplary embodiment of the present invention is shown below.

[0041] Figure 7 The NMR spectrum of the deuterated oseltamivir product prepared in an exemplary embodiment of the present invention is shown below.

[0042] Figure 8 This is a performance comparison diagram of different working electrode materials provided in an exemplary embodiment of the present invention for the preparation of deuterated acetic acid;

[0043] Figure 9 This is a performance comparison diagram of Cu and OD-Cu electrode materials provided in an exemplary embodiment of the present invention for the preparation of deuterated acetic acid;

[0044] Figure 10 This is a scanning electron microscope (SEM) image of the working electrode Cu NRs provided in an exemplary embodiment of the present invention. Detailed Implementation

[0045] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0046] In the description of this invention, it should be noted that the directions or positional relationships indicated by terms such as "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer" are based on the directions or positional relationships shown in the accompanying drawings and are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0047] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to fixed connections, detachable connections, or integral connections; they can refer to mechanical connections or electrical connections; they can refer to direct connections or indirect connections through an intermediate medium; and they can refer to the internal communication between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0048] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0049] First, it should be noted that deuterated acetic acid is currently mainly prepared by the hydrolysis of acetic anhydride, a high-temperature exothermic reaction that is prone to danger. It also suffers from low yield, high cost, and difficulty in catalyst recovery.

[0050] In this exemplary embodiment, a highly efficient electrosynthetic method for deuterated acetic acid using D2O as a deuterium source is provided, comprising the following steps:

[0051] In a standard three-electrode two-chamber electrolysis system, deuterated water is used as the deuterium source, and electrolytes and surfactants are added. Trichloroacetic acid is reduced to deuterated acetic acid by constant current electrolysis.

[0052] Among them, the single metal electrode of the in-situ grown nanorod is the working electrode in the standard three-electrode system.

[0053] Specifically, this invention is the first to achieve the electrocatalytic dehalogenation of trichloroacetic acid to prepare deuterated acetic acid under room temperature conditions, the reaction principle of which is as follows: Figure 1 As shown. Trichloroacetic acid is a harmful substance in industrial wastewater. Dehalogenating and deuterating trichloroacetic acid, followed by further acylation, is a feasible route for preparing deuterated acetamide compounds, and also provides new guidance for wastewater treatment and environmental protection. Aqueous-phase electrocatalytic organic synthesis has advantages such as environmental friendliness, mild reaction conditions, and high cost-effectiveness, and is an emerging and efficient method for preparing organic products. Using deuterated water as a deuterium source, the active deuterium generated by the decomposition of deuterated water can be utilized in situ during the electrocatalytic process, thereby achieving deuteration modification of organic matter.

[0054] This method boasts high conversion and selectivity, making it a highly efficient synthetic approach. Furthermore, it utilizes inexpensive deuterium-water as the deuterium source, employs mild reaction conditions, eliminates the need for high temperature and pressure, simplifies operation, facilitates product separation, and allows for catalyst reuse. This provides a green, safe, and efficient method for the synthesis of deuterated acetyl drugs, effectively avoiding the problems associated with other synthetic methods, such as the use of precious metal catalysts, expensive deuterium gas and deuterated organic reagents, complex operation, long reaction times, and low deuteration rates.

[0055] More preferably, in an exemplary embodiment, the standard three-electrode two-chamber electrolysis system includes:

[0056] The working electrode was a copper metal electrode with in-situ grown nanorods, the reference electrode was Hg / HgO, and the counter electrode was a Pt sheet.

[0057] The H-type dual-chamber standard three-electrode electrolytic cell is a container in which the cathode electrolysis chamber and the anolyte electrolysis chamber are separated by a proton exchange membrane. In a specific exemplary embodiment, the proton exchange membrane used is a Nafion membrane. TM 117.

[0058] Specifically, in this exemplary embodiment, the present invention uses copper nanorods (CuNRs) obtained by in-situ electroreduction of copper oxide as the working electrode, mercury / mercury oxide (Hg / HgO) as the reference electrode, and a Pt sheet as the counter electrode. The electrolytic solution is a two-chamber standard three-electrode electrolysis system containing a deuterated aqueous solution of 0.5 M K₂CO₃ and 0.75 mM n-octyltrimethylammonium bromide (OTAB). Deuterated acetic acid compounds are prepared by highly selective reduction of trichloroacetic acid via constant current electrolysis. This provides a green, safe, and efficient method for synthesizing deuterated acetyl drugs and building blocks, and has broad application prospects.

[0059] More preferably, in an exemplary embodiment, the addition of an electrolyte and a surfactant to reduce trichloroacetic acid to deuterated acetic acid via constant current electrolysis includes:

[0060] Add the reaction substrate, electrolyte, surfactant, and deuterium water to the cathode electrolysis chamber, and add the electrolyte and deuterium water to the anolyte electrolysis chamber;

[0061] A reaction solution containing deuterated acetic acid was prepared by constant current electrolysis.

[0062] The reaction solution was distilled, and the product was collected at 118°C to obtain deuterated acetic acid.

[0063] Specifically, in this exemplary embodiment, a constant current electrolysis method is used, with a current density of 100 mA / cm². -2 Its conversion rate is as high as 95%, selectivity as high as 91%, Faraday efficiency as high as 87%, and deuteration rate as high as 99%.

[0064] More preferably, in an exemplary embodiment, the electrolyte is an alkali and / or an alkali salt;

[0065] The surfactant is n-octyltrimethylammonium bromide.

[0066] More preferably, in an exemplary embodiment, the electrolyte is one or more of sodium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide; further, the electrolyte is potassium carbonate.

[0067] The electrolyte concentration is 0.1–1.5 mol / L; more specifically, the electrolyte concentration is 0.5 mol / L.

[0068] In a specific exemplary embodiment of the present invention, the electrolytes of both the cathode and the anolyte are potassium carbonate with a concentration of 0.5 mol / L; and the concentration of n-octyltrimethylammonium bromide is 0.5–1.0 mmol / L.

[0069] It should be noted that the purpose of adding a surfactant to the cathode electrolysis cell is to construct a hydrophobic microenvironment on the catalyst surface. In a specific embodiment of the present invention, the surfactant used is n-octyltrimethylammonium bromide (OTAB), and the reaction has good yield and Faraday efficiency when its concentration is 0.75 mM.

[0070] All the above electrocatalytic reactions were carried out at room temperature, with a reaction temperature of 15–40°C, a reaction charge of 100–500°C, and a reaction time of 30–50 min; further, the reaction temperature was 20–25°C, the reaction charge was 300°C, and the reaction time was 50 min.

[0071] See Figure 2 Exemplary embodiments of the present invention compared the conversion rate, selectivity, and faradaic efficiency of the reaction with and without different surfactants. The results showed that the reaction exhibited the best overall performance when using OTAB. Using surfactants can effectively improve the reaction selectivity and faradaic efficiency of the electrocatalytic preparation of deuterated acetic acid using D2O as a deuterium source.

[0072] Specific Example 1: Synthesis of Deuterated Acetic Acid:

[0073] An H-type electrolytic cell was used as the container, with the cathode and anode chambers separated by an ion-exchange membrane. 6 mL of a deuterium aqueous solution containing 0.5 M K₂CO₃ and 0.75 mM OTAB was added to the cathode chamber, and 6 mL of a deuterium aqueous solution containing 0.5 M K₂CO₃ was added to the anode chamber. Then, 0.5 mmol of trichloroacetic acid was added to the cathode chamber, and the mixture was continuously stirred with a magnetic stirrer. CuNRs were used as the working electrode, a Pt sheet as the counter electrode, and an Hg / HgO (1.0 M KOH) electrode as the reference electrode. The cell was connected to an electrochemical workstation, and a constant current of -100 mA / cm² was selected. -2 After performing the theoretical coulombic test for the reaction, the cathode reaction solution was collected, and the products were qualitatively analyzed using NMR. The analysis showed that the conversion rate was 95%, the selectivity was 91%, the deuteration rate was 99%, and the Faraday efficiency was 87%. Figure 3 As shown in the figure. Finally, distillation yields the product deuterated acetic acid.

[0074] In another exemplary embodiment of the present invention, a method for efficient electrosynthesis of deuterated acetyl compounds using D2O as a deuterium source is provided, comprising the following steps:

[0075] Deuterated acetic acid is obtained by performing the efficient electrosynthesis method of deuterated acetic acid with D2O as the deuterium source as described in the previous exemplary embodiment;

[0076] Deuterated acetyl compounds were synthesized using deuterated acetic acid.

[0077] Specifically, in this exemplary embodiment, the present invention achieves the dechlorination of trichloroacetic acid, while simultaneously deuterating it and synthesizing a series of deuterated acetamide drugs, which has good economic feasibility and sustainability.

[0078] More preferably, in an exemplary embodiment, the deuterated acetyl compounds include deuterated aspirin, deuterated acetaminophen, deuterated celecoxib, and deoseltamivir.

[0079] Aspirin and paracetamol were synthesized directly, while celecoxib and oseltamivir were modified post-drugs.

[0080] Specific Example 2: Synthesis of Deuterated Aspirin:

[0081] 575 μL (10 mmol) of deuterated acetic acid (obtained in Example 1), 4 mL of DMAc (N,N-dimethylacetamide), and 6 mL of CH2Cl2 were added to a reaction flask. After dissolving by stirring at room temperature, the mixture was cooled to 0°C, and then 870 μL (12 mmol) of SOCl2 was slowly added dropwise, maintaining the reaction at 0°C for 20 min. Next, 973 μL (10 mmol) of salicylic acid was added, and the mixture was heated and maintained at 25°C for another 5 h. After the reaction was complete, 40 mL of distilled water and 40 mL of ethyl acetate were added sequentially to the reaction mixture. The mixture was transferred to a separatory funnel, and the aqueous layer was extracted with ethyl acetate (80 mL × 2). The combined organic layers were washed three times with 90 mL (2.5%) NaHCO3 aqueous solution and then washed twice with saturated brine (60 mL × 2). The organic layers were dried over anhydrous MgSO4, filtered, and the organic solvent was rotary evaporated to obtain crude deuterated aspirin. The crude product was further subjected to column chromatography (V(ethyl acetate):V(petroleum ether) = 1:1) to obtain a white solid pure product. Nuclear magnetic resonance (NMR) analysis showed a deuteration rate of 95%. Figure 4 As shown, the first one is 1 The second image is an HNMR spectrum. 13 C10 NMR spectrum.

[0082] Specific Example 3: Synthesis of Deuterated Paracetamol:

[0083] 575 μL (10 mmol) of deuterated acetic acid (obtained in Example 1), 4 mL of DMAc (N,N-dimethylacetamide), and 6 mL of CH2Cl2 were added to a reaction flask. After dissolving with stirring at room temperature, the mixture was cooled to 0°C, and then 870 μL (12 mmol) of SOCl2 was slowly added dropwise, maintaining the reaction at 0°C for 20 min. Next, 973 μL (10 mmol) of p-aminophenol was added, and the mixture was heated and maintained at 25°C for another 5 h. After the reaction was complete, 40 mL of distilled water and 40 mL of ethyl acetate were added sequentially to the reaction mixture. The mixture was transferred to a separatory funnel, and the aqueous layer was extracted with ethyl acetate (80 mL × 2). The combined organic layers were washed three times with 90 mL (2.5%) NaHCO3 aqueous solution and then washed twice with saturated brine (60 mL × 2). The organic layers were dried over anhydrous MgSO4, filtered, and the organic solvent was rotary evaporated to obtain crude deuterated p-acetaminophen. The crude product was further subjected to column chromatography (V(ethyl acetate):V(petroleum ether) = 1:1) to obtain a white solid pure product. Nuclear magnetic resonance (NMR) analysis showed a deuteration rate of 96%. Figure 5 As shown, the first one is 1 The second image is an HNMR spectrum. 13 C10 NMR spectrum.

[0084] Specific Implementation Example 4: Synthesis of Deuterated Celecoxib (Celebrex):

[0085] 575 μL (10 mmol) of deuterated acetic acid (obtained in Example 1), 4 mL of DMAc (N,N-dimethylacetamide), and 6 mL of CH2Cl2 were added to a reaction flask. After dissolving with stirring at room temperature, the mixture was cooled to 0°C, and then 870 μL (12 mmol) of SOCl2 was slowly added dropwise, maintaining the reaction at 0°C for 20 min. Next, 973 μL (10 mmol) of celecoxib was added, and the mixture was heated and maintained at 25°C for another 5 h. After the reaction was complete, 40 mL of distilled water and 40 mL of ethyl acetate were added sequentially to the reaction mixture. The mixture was transferred to a separatory funnel, and the aqueous layer was extracted with ethyl acetate (80 mL × 2). The combined organic layers were washed three times with 90 mL (2.5%) NaHCO3 aqueous solution and then washed twice with saturated brine (60 mL × 2). The organic layers were dried over anhydrous MgSO4, filtered, and the organic solvent was rotary evaporated to obtain crude deuterated celecoxib. The crude product was further subjected to column chromatography (V(ethyl acetate):V(petroleum ether) = 1:1) to obtain a white solid pure product. Nuclear magnetic resonance (NMR) analysis showed a deuteration rate of 95%. Figure 6 As shown, the first one is 1 The second image is an HNMR spectrum. 13 C10 NMR spectrum.

[0086] Specific Example 5: Synthesis of Deuterated Oseltamivir:

[0087] 575 μL (10 mmol) of deuterated acetic acid (obtained in Example 1), 4 mL of DMAc (N,N-dimethylacetamide), and 6 mL of CH2Cl2 were added to a reaction flask. After dissolving with stirring at room temperature, the mixture was cooled to 0°C, and then 870 μL (12 mmol) of SOCl2 was slowly added dropwise, maintaining the reaction at 0°C for 20 min. Next, 973 μL (10 mmol) of oseltamivir was added, and the mixture was heated and maintained at 25°C for another 5 h. After the reaction was complete, 40 mL of distilled water and 40 mL of ethyl acetate were added sequentially to the reaction mixture. The mixture was transferred to a separatory funnel, and the aqueous layer was extracted with ethyl acetate (80 mL × 2). The combined organic layers were washed three times with 90 mL (2.5%) NaHCO3 aqueous solution and then washed twice with saturated brine (60 mL × 2). The organic layers were dried over anhydrous MgSO4, filtered, and the organic solvent was rotary evaporated to obtain crude deuterated oseltamivir. The crude product was further subjected to column chromatography (V(ethyl acetate):V(petroleum ether) = 1:1) to obtain a white solid pure product. Nuclear magnetic resonance (NMR) analysis showed a deuteration rate of 98%. Figure 7 As shown, the first one is 1 The second image is an HNMR spectrum. 13 C10 NMR spectrum.

[0088] In another exemplary embodiment of the present invention, a working electrode is provided for use in the efficient electrosynthesis method of deuterated acetic acid with D2O as the deuterium source, or for use in the efficient electrosynthesis method of deuterated acetyl compounds with D2O as the deuterium source, wherein the working electrode comprises copper foam and copper nanorods grown in situ on the copper foam.

[0089] Specifically, in this exemplary embodiment, metallic copper is used as the working electrode of the present invention, which has good conversion rate and Faraday efficiency. For example... Figure 8 As shown, the electrode materials (Ti, Ni, Cu, CF, Pt, Fe) commonly used in various electrocatalytic methods were compared for the electrocatalytic preparation of deuterated acetic acid.

[0090] More preferably, in an exemplary embodiment, the working electrode is a CuNRs working electrode.

[0091] Specifically, in this exemplary embodiment, a comparison was made between a conventional Cu electrode and an OD-Cu (Oxide-derived Cu) electrode obtained by the reduction of Cu oxides. The results show that OD-Cu has better reaction selectivity, as shown in the attached figure. Figure 9As shown. Therefore, in this exemplary embodiment, the CuNRs electrode used is further specified to be an OD-Cu type electrode obtained by electrochemical reduction of Cu oxides. Only by using the CuNRs electrode material described in this exemplary embodiment can good reaction selectivity and Faraday efficiency be achieved.

[0092] More preferably, in an exemplary embodiment, the fabrication steps of the CuNRs working electrode include:

[0093] Copper foam pretreatment;

[0094] The pretreated copper foam was placed in a beaker containing a mixed solution of sodium hydroxide and ammonium persulfate, cooled in an ice-water bath for 2-4 hours, rinsed with ethanol and deionized water, and dried to obtain Cu(OH)2NRs.

[0095] The obtained Cu(OH)2NRs material was calcined at 60℃ for 2 hours in an argon atmosphere, then calcined at 120℃ for 4 hours, and finally calcined at 180℃ for 6 hours. After cooling to room temperature, it was washed with ethanol and deionized water and dried to obtain CuO NRs.

[0096] The obtained CuO NRs were used as the intermediate working electrode, Hg / HgO as the reference electrode, and a carbon rod as the counter electrode. A current of -50 mA was applied in an H-type electrolytic cell, and the electrolyte was a 0.5 M K₂CO₃ solution. Electrolysis was carried out for 10–30 minutes to obtain the Cu NRs working electrode (a method for preparing Cu NRs by in-situ electroreduction of CuO NRs). The SEM image of the CuNRs electrode is shown in the attached figure in the instruction manual. Figure 10 As shown.

[0097] Furthermore, the concentration of sodium hydroxide is 1–8 mol / L, and the concentration of ammonium persulfate is 0.2–1.0 mol / L; even further, the concentration of sodium hydroxide is 5 mol / L, and the concentration of ammonium persulfate is 0.2 mol / L; further still, the cooling reaction time is 3 h.

[0098] More preferably, in an exemplary embodiment, the copper foam pretreatment includes:

[0099] Soak the copper foam in acetone and ultrasonically clean it for 15 minutes to remove organic matter from the surface.

[0100] The foamed copper, from which surface organic matter has been removed, is placed in acid solution and ultrasonically cleaned for 15 minutes to remove surface oxides.

[0101] The copper foam with surface oxides removed is placed in deionized water and ultrasonically cleaned for 15 minutes to remove acetone and acid from the surface.

[0102] Specific Example 6: Preparation of Working Electrode

[0103] Preprocessing:

[0104] Step 1: Soak the copper foam in acetone and ultrasonically clean it for 15 minutes to remove organic matter from the surface.

[0105] Step 2: Place the copper foam obtained in Step 1 into an acid solution and ultrasonically clean it for 15 minutes to remove the surface oxides.

[0106] Step 3: Place the foamed copper obtained in Step 2 into deionized water and ultrasonically clean it for 15 minutes to remove acetone and acid from the surface.

[0107] The preparation method of copper nanorods (CuNRs) grown in situ on copper foam is carried out according to the following steps:

[0108] Step 1: Place the copper foam into a beaker containing a mixed solution of 5 mol / L sodium hydroxide and 0.2 mol / L ammonium persulfate, cool and react in an ice-water bath for 3 hours, rinse with ethanol and deionized water, and dry to obtain Cu(OH)2NRs;

[0109] Step 2: After drying, the material is calcined at 60°C for 2 hours in an argon atmosphere, then calcined at 120°C for 4 hours, and finally calcined at 180°C for 6 hours. After cooling to room temperature, it is rinsed with ethanol and deionized water and dried to obtain CuONRs.

[0110] The method for preparing CuNRs by in-situ electroreduction of CuO NRs is carried out according to the following steps: CuO NRs are used as the working electrode, Hg / HgO is used as the reference electrode, and a carbon rod is used as the counter electrode. A current of -50mA is applied in an H-type electrolytic cell, and the electrolyte is a 0.5M K2CO3 solution. Electrolysis is carried out for 10 to 30 minutes to obtain the CuNRs electrode.

[0111] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A highly efficient electrosynthetic method for deuterated acetic acid using D2O as a deuterium source, characterized in that: Includes the following steps: In a standard three-electrode two-chamber electrolysis system, deuterated water is used as the deuterium source, and electrolytes and surfactants are added. Trichloroacetic acid is reduced to deuterated acetic acid by constant current electrolysis. Among them, the single metal electrode of the in-situ grown nanorod is the working electrode in the standard three-electrode system.

2. The efficient electrosynthesis method for deuterated acetic acid using D2O as a deuterium source according to claim 1, characterized in that: The standard three-electrode two-chamber electrolysis system includes: The working electrode was a copper metal electrode with in-situ grown nanorods, the reference electrode was Hg / HgO, and the counter electrode was a Pt sheet. The H-type dual-chamber standard three-electrode electrolytic cell is the container, with the cathode electrolytic chamber and the anode electrolytic chamber separated by a proton exchange membrane.

3. The efficient electrosynthesis method for deuterated acetic acid using D2O as a deuterium source according to claim 2, characterized in that: The process of adding electrolytes and surfactants to reduce trichloroacetic acid to deuterated acetic acid via constant current electrolysis includes: Add the reaction substrate, electrolyte, surfactant, and deuterium water to the cathode electrolysis chamber, and add the electrolyte and deuterium water to the anolyte electrolysis chamber; A reaction solution containing deuterated acetic acid was prepared by constant current electrolysis. The reaction solution was distilled to obtain the product deuterated acetic acid.

4. The efficient electrosynthesis method for deuterated acetic acid using D2O as a deuterium source according to claim 3, characterized in that: The electrolyte is an alkali and / or an alkali salt; The surfactant is n-octyltrimethylammonium bromide.

5. A highly efficient electrosynthetic method for deuterated acetyl compounds using D2O as the deuterium source, characterized in that: Includes the following steps: Deuterated acetic acid is obtained by performing the efficient electrosynthesis method of deuterated acetic acid using D2O as a deuterium source as described in any one of claims 1 to 4; Deuterated acetyl compounds were synthesized using deuterated acetic acid.

6. The efficient electrosynthesis method for deuterated acetyl compounds using D2O as a deuterium source according to claim 5, characterized in that: The deuterated acetyl compounds include deuterated aspirin, deuterated acetaminophen, deuterated celecoxib, and deuterated oseltamivir.

7. A working electrode, applied to the efficient electrosynthesis method of deuterated acetic acid using D2O as a deuterium source as described in any one of claims 1 to 4, or applied to the efficient electrosynthesis method of deuterated acetyl compounds using D2O as a deuterium source as described in any one of claims 5 to 6, characterized in that: The working electrode comprises copper foam and copper nanorods grown in situ on the copper foam.

8. The working electrode according to claim 7, characterized in that: The working electrode is a CuNRs working electrode.

9. The working electrode according to claim 8, characterized in that: The preparation steps of the CuNRs working electrode include: Copper foam pretreatment; The pretreated copper foam was placed in a beaker containing a mixed solution of sodium hydroxide and ammonium persulfate, cooled in an ice-water bath for 2-4 hours, rinsed with ethanol and deionized water, and dried to obtain Cu(OH)2NRs. The obtained Cu(OH)2NRs material was calcined at 60℃ for 2 hours in an argon atmosphere, then calcined at 120℃ for 4 hours, and finally calcined at 180℃ for 6 hours. After cooling to room temperature, it was washed with ethanol and deionized water and dried to obtain CuO NRs. The obtained CuO NRs were used as the intermediate working electrode, Hg / HgO as the reference electrode, and a carbon rod as the counter electrode. A current of -50mA was applied in an H-type electrolytic cell, and the electrolyte was a 0.5M K2CO3 solution. Electrolysis was carried out for 10 to 30 minutes to obtain the Cu NRs working electrode.

10. The working electrode according to claim 8, characterized in that: The copper foam pretreatment includes: The copper foam was immersed in acetone and ultrasonically cleaned to remove organic matter from the surface. The foamed copper, from which surface organic matter has been removed, is placed in an acid solution for ultrasonic cleaning to remove surface oxides. The copper foam with surface oxides removed is ultrasonically cleaned in deionized water to remove acetone and acid from the surface.

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