Method for directly synthesizing fumaric acid and succinic acid derivatives from CO2
By using an electrochemical method to react aromatic yne compounds with carbon dioxide under mild conditions without metals or catalysts, fumaric acid and succinic acid derivatives were successfully synthesized. This solved the problems of high temperature and high pressure and noble metal catalysis in existing technologies, realizing an efficient and green synthetic route and expanding its application fields.
Patent Information
- Application Number
- CN202511740662.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-25
- Publication Date
- 2026-02-10
AI Technical Summary
Existing technologies struggle to efficiently activate carbon dioxide and selectively synthesize high-value-added carboxylic acid products, especially fumaric acid and succinic acid derivatives, under mild conditions. Traditional methods suffer from problems such as high temperature and pressure, precious metal catalysts, and the generation of large amounts of wastewater.
An electrochemical method was used to synthesize fumaric acid and succinic acid derivatives in a carbon dioxide atmosphere via an electrochemical dicarboxylation reaction under conditions of no metals, no external catalysts, no reducing agents, and no ligands, using aromatic yne compounds as raw materials. Electrolysis was carried out using magnesium and carbon electrodes, with acetonitrile or DMF as solvents, and the current and electrolysis conditions were controlled.
This method enables the high-conversion and high-selectivity synthesis of various fumaric acid and succinic acid derivatives under mild conditions, providing a green and efficient synthetic route suitable for the preparation of bioactive molecular derivatizations and expanding their application scope.
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Figure CN121496413A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a method for directly synthesizing fumaric acid and succinic acid derivatives from CO2. BACKGROUND
[0002] Alkynes are an important class of fine chemicals, which are mainly produced on an industrial scale through the hydrolysis of calcium carbide (CaC2); and calcium carbide itself is obtained by the reaction of coal and lime in an electric arc furnace. Therefore, the functionalization reaction of alkynes is one of the key ways to convert coal-based raw materials into high-value fine chemicals, and has been widely concerned by the industry and academia for a long time. Among the many functionalization strategies, the direct carboxylation of alkynes with carbon dioxide is considered to be a high-atom-economy and simple-step synthesis route of carboxylic acid derivatives due to the characteristics of CO2, such as wide source, renewable, and non-toxic.
[0003] In recent years, the synthesis of carboxylic acids from cheap alkynes and carbon dioxide has shown significant advantages in environmental friendliness and economy, especially the method of directly carboxylating terminal alkynes with CO2 to prepare 3-aryl acrylic acid has been intensively studied. However, due to the thermodynamic stability and kinetic inertness of CO2 itself, it is still a great challenge to achieve its efficient activation and high-selectivity synthesis of high-value carboxylic acid products under mild conditions, and the related methodology research also needs further development. Electrochemical synthesis as a green and flexible reaction strategy has been increasingly valued in organic synthesis, which can achieve the effective activation of CO2 under mild conditions by adjusting the current or voltage, thus providing a possible solution to the above problems.
[0004] In summary, it is of important theoretical value and practical significance to develop a new method for directly synthesizing dicarboxylic acid compounds from CO2 under mild electrochemical conditions. SUMMARY
[0005] Therefore, the application discloses a method for directly synthesizing fumaric acid and succinic acid derivatives from CO2, which is a new method for synthesizing fumaric acid and succinic acid derivatives from CO2 under electrochemical conditions with high conversion rate and high selectivity by taking aryl alkynes as raw materials in an air atmosphere, and expands the application of fumaric acid and succinic acid derivatives in the derivation of bioactive molecules.
[0006] It should be noted that based on the research basis in electrochemistry and free radical chemistry, the electrochemical dicarboxylation of alkynes and carbon dioxide is realized for the first time under mild conditions without metal, external catalyst, reducing agent, ligand, and additive. Through systematic optimization of substrates, solvents, and electrolysis conditions, the strategy of the application can synthesize various fumaric acid and succinic acid derivatives with good yield and high selectivity.
[0007] To achieve the above objectives, the present invention adopts the following technical solution:
[0008] A method for the direct synthesis of fumaric acid and succinic acid derivatives from CO2 uses aromatic yne compound 1 as a reaction substrate to obtain fumaric acid and succinic acid derivative 3 under electrochemical conditions and a CO2 atmosphere; the synthetic route is shown in the following reaction formula:
[0009]
[0010] In this invention, R 1 This refers to one or more substituents at different positions such as ortho, meta, and para on the benzene ring, specifically one or more of the following: C1-C10 alkyl, C1-C10 ester, methoxy, carbonyl, trifluoromethyl, cyano, halogen, and benzyl; preferably one or more of the following: methyl, methoxy, fluorine, chlorine, and bromine.
[0011] R 2 It represents hydrogen, C1-C10 alkyl and substituted aryl groups, wherein the substituents in the substituted aryl groups include one or more of methoxy, fluorine, chlorine, bromine, trifluoromethyl, cyano, nitro, and ester groups.
[0012] In this invention, the reaction temperature is room temperature and the reaction time is 3 hours.
[0013] In this invention, the reaction gas atmosphere is carbon dioxide, the selected positive electrode is a magnesium electrode (10mm×20mm×0.5mm), the negative electrode is a carbon electrode (10mm×20mm×1mm), and the current used is 8-10mA.
[0014] In this invention, the selected electrolytic cell is a non-separated electrolytic cell, and the selected electrolyte is... n Bu4NI、 n One of Bu4NPF6.
[0015] In this invention, the reaction solvent is one of acetonitrile and DMF.
[0016] Preferably, a method for directly synthesizing fumaric acid derivatives from CO2 includes the following steps:
[0017] Will nBu4NPF6 (0.1 mmol) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were installed in the reaction tube, and the tube was evacuated and filled with CO2 three times. Then, aromatic yne compounds (0.2 mmol) and DMF (3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was carefully quenched with HCl (2 mL), extracted three times with ethyl acetate (3 × 20 mL), dried with anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude residue was purified by rapid column chromatography using petroleum ether / ethyl acetate / acetic acid (v / v / v = 15 / 1 / 0.001-3 / 1 / 0.001) to obtain fumaric acid derivatives.
[0018] Preferably, a method for directly synthesizing succinic acid derivatives from CO2 includes the following steps:
[0019] Will n Bu4NI (0.1 mmol) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were installed in the reaction tube, and the tube was evacuated and filled with CO2 three times. Then, an aromatic yne compound (0.2 mmol) and CH3CN (3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 8 mA for 3 hours at room temperature. The mixture was carefully quenched with HCl (2 mL), extracted three times with ethyl acetate (3 × 20 mL), dried with anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude residue was purified by rapid column chromatography using petroleum ether / ethyl acetate / acetic acid (v / v / v = 15 / 1 / 0.001-3 / 1 / 0.001) to obtain a succinic acid derivative.
[0020] Compared with the prior art, the beneficial effects of the present invention are:
[0021] 1) Based on experimental research, this invention provides a novel method for the direct preparation of fumaric acid and succinic acid derivatives from aromatic yne compounds with CO2 under mild electrochemical conditions. This method features a broad substrate range, scalability, no need for additional reducing agents, no hydrogen donors, no metals, no ligands, and mild conditions. This electrochemical carbon capture and conversion strategy provides a new pathway for the high-value utilization of CO2 and can effectively prepare acid intermediates for the synthesis of various natural products and drug molecules.
[0022] It should be noted that succinic acid compounds (including fumaric acid and succinic acid backbones) have wide and important applications in many industrial fields, including: 1. Key monomers for biodegradable plastics [such as polybutylene succinate (PBS) and polybutylene terephthalate-adipate-succinate (PBAT)]; 2. Acidity regulators and flavor enhancers in food; 3. Key precursors for the synthesis of environmentally friendly solvents 1,4-butanediol (BDO), tetrahydrofuran (THF), and succinimide; 4. Anionic surfactants succinate sulfonates in detergents and personal care products; 5. Electroplating additives and photosensitive chemicals, etc.
[0023] In addition, trans-fumaric acid is used to produce unsaturated polyester resins, which are characterized by good chemical corrosion resistance and heat resistance; ferric fumarate is a drug called ferrous sulfate used to treat microcytic anemia; the monosodium salt produced by the reaction of trans-fumaric acid with sodium hydroxide can be used not only as a sour condiment, but also as an intermediate for the synthesis of resins and mordants.
[0024] 2) Currently, the main synthetic processes for fumaric acid and succinic acid derivatives rely on the reaction of benzene or n-butane under high temperature and pressure, catalyzed by metal oxides, to produce maleic anhydride. The maleic anhydride is then hydrolyzed to produce fumaric acid, which is further reduced by hydrogenation to produce succinic acid. Although this process has been successfully applied in industrial production, problems such as the use of precious metal catalysts, harsh high-temperature and high-pressure conditions, the generation of large amounts of wastewater, and the limited variety of products make it essential to seek a greener synthetic method for fumaric acid and succinic acid derivatives. In comparison, this invention uses aromatic yne compounds and CO2 as raw materials, with mild conditions, no need for additional reducing agents, no hydrogen donors, no metals, and no ligands, providing a green and efficient new method for the preparation of fumaric acid and succinic acid derivatives. Attached Figure Description
[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0026] Figure 1 These are the 1H NMR spectrum (a) and 1C NMR spectrum (b) of 2,3-diphenylfumaric acid 2a.
[0027] Figure 2 This is the 1H NMR and 1C NMR spectrum of 2-(4-ethylphenyl)-3-(p-tolyl)fumaric acid 2b.
[0028] Figure 3This is the 1H NMR and 1C NMR spectrum of 2-(4-butylphenyl)-3-(4-methoxyphenyl)fumaric acid 2c.
[0029] Figure 4 This is the 1H NMR and 1C NMR spectrum of 2-(4-ethoxyphenyl)-3-(4-propylphenyl)fumaric acid 2d.
[0030] Figure 5 The NMR spectrum (C1, C1, and fluorine spectrum) of 2-(4-fluorophenyl)-3-(4-propylphenyl)fumaric acid (2e) is shown in Figure 2.
[0031] Figure 6 This is the 1H NMR and 1C NMR spectrum of 2-([1,1'-biphenyl]-4-yl)fumaric acid 2f.
[0032] Figure 7 This is the 1H NMR and 1C NMR spectrum of 2g of 2-(4'-ethyl-[1,1'-biphenyl]-4-yl)fumaric acid.
[0033] Figure 8 This is the 1H and 1C NMR spectrum of 2-(4'-propyl-[1,1'-biphenyl]-4-yl)fumaric acid.
[0034] Figure 9 This is the 1H NMR and 1C NMR spectrum of 2-([1,1'-biphenyl]-4-yl)succinic acid 2i.
[0035] Figure 10 This is the 1H NMR and 1C NMR spectrum of 2-(4'-ethyl-[1,1'-biphenyl]-4-yl)succinic acid 2j.
[0036] Figure 11 This is the 1H NMR and 1C NMR spectrum of 2-(4'-propyl-[1,1'-biphenyl]-4-yl)succinic acid at 2k. Detailed Implementation
[0037] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0038] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.
[0039] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.
[0040] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.
[0041] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.
[0042] This invention discloses a method for directly synthesizing fumaric acid and succinic acid derivatives from CO2.
[0043] To better understand the present invention, the following embodiments are provided for further detailed description of the present invention, but they should not be construed as limiting the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are also considered to fall within the protection scope of the present invention.
[0044] Example 1
[0045] Synthesis of 2,3-diphenylfumaric acid 2a
[0046] Will n Bu4NPF6 (CAS: 3109-63-5, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled three times with CO2. Then, diphenylacetylene (CAS: 501-65-5, 1a, 0.2 mmol) and DMF (CAS: 68-12-2, 3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography using petroleum ether / ethyl acetate / acetic acid to give fumaric acid 2a in 79% yield.
[0047] 1 H NMR (600MHz, DMSO-d6) δ7.43~7.38(m,10H). 13C NMR (151MHz, DMSO-d6) δ169.34,136.02,135.78,128.59,128.54,127.78.
[0048] Example 2
[0049] Synthesis of 2-(4-ethylphenyl)-3-(p-tolyl)fumaric acid 2b
[0050] Will n Bu4NPF6 (CAS: 3109-63-5, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled three times with CO2. Then, 1-ethyl-4-(p-tolylethynyl)benzene (CAS: 22692-80-4, 1b, 0.2 mmol) and DMF (3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography in petroleum ether / ethyl acetate / acetic acid to give fumaric acid 2b in 65% yield.
[0051] 1 H NMR (600MHz, DMSO-d6) δ13.04 (s, 2H), 7.33~7.30 (m, 4H), 7.26 (d, J = 8.1Hz, 2H) ,7.23(d,J=8.0Hz,2H),2.65~2.62(m,2H),2.33(s,3H),1.21(t,J=7.6Hz,3H). 13 CNMR(151MHz,DMSO-d6)δ169.57,144.19,138.03,135.34,135.27,133.20,1 32.94,129.07,127.89,127.72,127.62,27.92,20.82,15.38.HRMS(ESI):m / z calcd for C 19 H 18 O4K[M+K + ]:349.0837; found:349.0839.HRMS(ESI):m / zcalcd for C 19 H 18 O4Na[M+Na + ]:333.1097; found:333.1096.
[0052] Example 3
[0053] Synthesis of 2-(4-Butylphenyl)-3-(4-methoxyphenyl)fumaric acid 2c
[0054] Will n Bu4NPF6 (CAS: 3109-63-5, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled three times with CO2. Then, 1-butyl-4-((4-methoxyphenyl)ethynyl)benzene (CAS: 35684-12-9, 1c, 0.2 mmol) and DMF (3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography in petroleum ether / ethyl acetate / acetic acid to give fumaric acid 2c in 85% yield.
[0055] 1 H NMR(600MHz,DMSO-d6)δ13.06(s,2H),7.33~7.29(m,4H),7.23(d,J=7.9Hz,2H),6.97(d,J=8.8Hz,2 H), 3.78 (s, 3H), 2.59 (t, J = 7.8Hz, 2H), 1.59 ~ 1.54 (m, 2H), 1.35 ~ 1.29 (m, 2H), 0.91 (t, J = 7.3Hz, 3H). 13 C NMR(151MHz,DMSO-d6)δ169.69,159.39,142.74,135.02,134.69,133.23,129.10,1 28.36,128.01,127.63,113.92,55.20,34.57,32.97,21.84,13.79.HRMS(ESI):m / z calcd for C 21 H 22 O5K[M+K + ]:393.1099;found:393.1093.
[0056] Example 4
[0057] Synthesis of 2-(4-ethoxyphenyl)-3-(4-propylphenyl)fumaric acid 2d
[0058] Will nBu4NPF6 (CAS: 3109-63-5, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled three times with CO2. Then, 1-ethoxy-4-((4-propylphenyl)ethynyl)benzene (CAS: 39969-29-4, 1d, 0.2 mmol) and DMF (3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography in petroleum ether / ethyl acetate / acetic acid to give fumaric acid 2d in 89% yield.
[0059] 1 H NMR(600MHz,DMSO-d6)δ13.04(s,1H),7.33~7.30(m,4H),7.23(d,J=8.3Hz,2H),6.96(d,J=8.8Hz,2H), 4.06~4.03(m,2H),2.58~2.56(m,2H),1.64~1.58(m,2H),1.34(t,J=7.0Hz,3H),0.91(t,J=7.3Hz,3H). 13 C NMR(151MHz,DMSO-d6)δ170.19,170.17,159.16,142.99,135.52,135.04,133.75,129.55, 128.87,128.29,128.08,114.79,63.61,37.45,24.40,15.09,14.18.HRMS(ESI):m / zcalcd for C 21 H 22 O5Na[M+Na + ]: 377.1359; found: 377.1354.
[0060] Example 5
[0061] Synthesis of 2-(4-fluorophenyl)-3-(4-propylphenyl)fumaric acid 2e
[0062] Will nBu4NPF6 (CAS: 3109-63-5, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled three times with CO2. Then, 1-fluoro-4-((4-propylphenyl)ethynyl)benzene (CAS: 145698-32-4, 1e, 0.2 mmol) and DMF (3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography in petroleum ether / ethyl acetate / acetic acid to give fumaric acid 2e in 87% yield.
[0063] 1 H NMR (600MHz, DMSO-d6) δ13.18 (s, 1H), 7.46~7.44 (m, 2H), 7.34 (d, J = 8.2Hz, 2H), 7.28~7.24(m,4H),2.59~2.57(m,2H),1.64~1.58(m,2H),0.91(t,J=7.3Hz,3H). 13 CNMR(151MHz,DMSO-d6)δ169.39,169.33,162.14(d,J=244.6Hz),142.88,136.59,134.41,132.97,13 2.36(d,J=3.2Hz),130.10(d,J=9.1Hz),128.52,127.72,115.52(d,J=21.1Hz),37.07,24.00,13.77. 19 F NMR(565MHz,DMSO-d6)δ-35.19.HRMS(ESI):m / z calcdfor C 19 H 18 O4[M+H + ]:329.1125; found:329.1184.
[0064] Example 6
[0065] Synthesis of 2-([1,1'-biphenyl]-4-yl)fumaric acid 2f
[0066] Will nBu4NPF6 (CAS: 3109-63-5, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled with CO2 three times. 4-Phenylacetylene (CAS: 29079-00-3, 1f, 0.2 mmol) and DMF (3.0 mL) were then added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography in petroleum ether / ethyl acetate / acetic acid to give fumaric acid 2f in 80% yield.
[0067] 1 H NMR(600MHz,DMSO-d6)δ13.08(s,2H),7.70(d,J=7.0Hz,2H),7.66(d,J=8.3Hz,2H) ,7.48(t,J=7.8Hz,2H),7.38(t,J=7.3Hz,1H),7.35(d,J=8.3Hz,2H),6.97(s,1H). 13 C NMR(151MHz,DMSO-d6)δ167.51,166.73,141.56,139.82,139.71,133.76,129.97,129.67,129.03,127.66,126.70,125.89.HRMS(ESI):m / z calcd for C 16 H 12 O4K[M+K + ]:307.0367; found:307.0366.
[0068] Example 7
[0069] Synthesis of 2g of 2-(4'-ethyl-[1,1'-biphenyl]-4-yl)fumaric acid
[0070] Will nBu4NPF6 (CAS: 3109-63-5, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled three times with CO2. Then, 4-ethylphenylphenylacetylene (CAS: 477587-89-6, 1 g, 0.2 mmol) and DMF (3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2 N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography using petroleum ether / ethyl acetate / acetic acid to give 2 g of fumaric acid in 66% yield.
[0071] 1 H NMR (600MHz, DMSO-d6) δ13.11(s,2H),7.62(dd,J=11.7,8.1Hz,4H),7.33~7.31(m,4H),6.95(s,1H),2.67~2.63(m,2H),1.21(t,J=7.6Hz,3H). 13 CNMR(151MHz,DMSO-d6)δ167.51,166.72,143.29,141.56,139.77,137.08,133. 39,129.84,129.60,128.43,126.59,125.62,27.83,15.55.HRMS(ESI):m / zcalcd for C 18 H 16 O4Na[M+Na + ]:319.0941; found:310.0940.
[0072] Example 8
[0073] Synthesis of 2-(4'-propyl-[1,1'-biphenyl]-4-yl)fumaric acid 2h
[0074] Will nBu4NPF6 (CAS: 3109-63-5, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled with CO2 three times. 4-Propanylphenylacetylene (CAS: 360768-57-6, 1 h, 0.2 mmol) and DMF (3.0 mL) were then added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 h at room temperature. The mixture was then carefully quenched with HCl (2 N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography using petroleum ether / ethyl acetate / acetic acid to give fumarate compounds for 2 h, in 66% yield.
[0075] 1 H NMR (600MHz, DMSO-d6) δ7.61 (dd, J=14.0, 8.3Hz, 4H), 7.37~7.29 (m, 4H), 6.93 (s, 1H), 2.60 (t, J=7.4Hz, 2H), 1.66~1.60 (m, 2H), 0.92 (t, J=7.3Hz, 3H). 13 C NMR(151MHz,DMSO-d6)δ167.47,166.68,141.64,141.49,139.71,137.04,133.3 5,129.80,129.56,128.97,126.47,125.58,36.87,24.01,13.68.HRMS(ESI):m / z calcd for C 19 H 18 O4K[M+K + ]:349.0837; found:349.0834.
[0076] Example 9
[0077] Synthesis of 2-([1,1'-biphenyl]-4-yl)succinic acid 2i
[0078] Will nBu4NI (CAS: 311-28-4, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled with CO2 three times. 4-Phenylacetylene (CAS: 29079-00-3, 1i, 0.2 mmol) and CH3CN (3.0 mL) were then added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 8 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography using petroleum ether / ethyl acetate / acetic acid to give succinic acid 2i in 68% yield.
[0079] 1 H NMR (600MHz, DMSO-d6) δ12.40(s,1H),7.63(dd,J=12.9,7.0Hz,4H),7.46(t,J=7.6Hz,2H),7.40~7.3 5(m,3H),3.95(dd,J=10.1,5.2Hz,1H),3.00(dd,J=16.9,10.1Hz,1H),2.60(dd,J=16.9,5.2Hz,1H). 13 C NMR(151MHz,DMSO-d6)δ173.94,172.63,139.77,139.10,137.85,128.93,128.33,127.43,126.91,126.62,46.50,37.32.HRMS(ESI):m / z calcd for C 16 H 14 O4K[M+K + ]:309.0523; found:309.0520.
[0080] Example 10
[0081] Synthesis of 2-(4'-ethyl-[1,1'-biphenyl]-4-yl)succinic acid 2j
[0082] Will nBu4NI (CAS: 311-28-4, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled three times with CO2. Then, 4-ethylphenylphenylacetylene (CAS: 477587-89-6, 1j, 0.2 mmol) and CH3CN (3.0 mL) were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 8 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography in petroleum ether / ethyl acetate / acetic acid to give 2j of succinic acid in 60% yield.
[0083] 1 H NMR (600MHz, DMSO-d6) δ12.39(s,2H),7.60(d,J=8.3Hz,2H),7.56(d,J=8.2Hz,2H),7.37(d,J=8.3Hz,2H),7.29(d,J =8.2Hz,2H),3.95(dd,J=10.1,5.1Hz,1H),3.00(dd,J=17.0,10.3Hz,1H),2.65~2.58(m,3H),1.20(t,J=7.6Hz,3H). 13 C NMR(151MHz,DMSO-d6)δ173.99,172.67,143.07,139.10,137.53,137.18,1 28.35,128.30,126.70,126.54,46.51,37.35,27.81,15.57.HRMS(ESI):m / z calcd for C 18 H 18 O4K[M+K + ]:337.0837; found:337.0838.
[0084] Example 11
[0085] Synthesis of 2-(4'-propyl-[1,1'-biphenyl]-4-yl)succinic acid 2k
[0086] Will nBu4NI (CAS: 311-28-4, 0.1 mmol, 0.5 eq.) was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were then installed in the reaction tube, and the tube was evacuated and filled three times with CO2. 4-Propanylphenylacetylene (CAS: 360768-57-6, 1 kJ, 0.2 mmol) and CH3CN (3.0 mL) were then added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 8 mA for 3 hours at room temperature. The mixture was then carefully quenched with HCl (2 N, 2 mL), extracted three times with ethyl acetate (3 × 20 mL), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the crude residue was purified by rapid column chromatography in petroleum ether / ethyl acetate / acetic acid to give 2 kJ of succinic acid in 83% yield.
[0087] 1 H NMR (600MHz, DMSO-d6) δ12.39(s,2H),7.60(d,J=8.3Hz,2H),7.55(d,J=8.2Hz,2H),7.37(d,J=8.3Hz,2H),7.26(d,J=8.2Hz,2 H),3.95(dd,J=10.2,5.2Hz,1H),3.00(dd,J=16.9,10.2Hz,1H),2.62~2.57(m,3H),1.64~1.58(m,2H),0.91(t,J=7.3Hz,3H). 13 C NMR (151MHz, DMSO-d6) δ174.00,172.67,141.46,139.08,137.53,137.18,128. 93,128.29,126.69,126.45,46.51,37.35,36.89,24.05,13.69.HRMS(ESI):m / z calcd forC 19 H 20 O4K[M+K + ]:351.0993; found:351.0990.
[0088] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A method for directly synthesizing fumaric acid and succinic acid derivatives from CO2, characterized in that, Using aromatic acetylenic compound 1 as a reaction substrate, fumaric acid and succinic acid derivative 3 were obtained under electrochemical conditions in a CO2 atmosphere; The synthetic route is shown in the following reaction equation: Among them, R 1 This indicates one or more substituents at different positions (ortho, meta, para) on the benzene ring, specifically one or more of C1-C10 alkyl, C1-C10 ester, methoxy, carbonyl, trifluoromethyl, cyano, halogen, and benzyl; R 2 It represents hydrogen, C1-C10 alkyl and substituted aryl groups, wherein the substituents in the substituted aryl groups include one or more of methoxy, fluorine, chlorine, bromine, trifluoromethyl, cyano, nitro and ester groups.
2. The method for directly synthesizing fumaric acid and succinic acid derivatives from CO2 according to claim 1, characterized in that, R 1 It is selected from one or more of methyl, methoxy, fluorine, chlorine, and bromine.
3. The method for directly synthesizing fumaric acid and succinic acid derivatives from CO2 according to claim 1, characterized in that, The reaction temperature was room temperature, and the reaction time was 3 hours.
4. The method for directly synthesizing fumaric acid and succinic acid derivatives from CO2 according to claim 1, characterized in that, The reaction gas atmosphere is carbon dioxide; the positive electrode is a magnesium electrode with dimensions of 10mm×20mm×0.5mm, and the negative electrode is a carbon electrode with dimensions of 10mm×20mm×1mm; the current is 8-10mA.
5. The method for directly synthesizing fumaric acid and succinic acid derivatives from CO2 according to claim 1, characterized in that, The electrolytic cell is a non-separated electrolytic cell, and the electrolyte is... n Bu4NI、 n One of Bu4NPF6.
6. The method for directly synthesizing fumaric acid and succinic acid derivatives from CO2 according to claim 1, characterized in that, The reaction solvent is either acetonitrile or DMF.
7. The method for directly synthesizing fumaric acid and succinic acid derivatives from CO2 according to claim 1, characterized in that, 0.1 mmol n Bu4NPF6 was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were installed in the reaction tube, and the tube was evacuated and filled with CO2 three times. Then, 0.2 mmol of an aromatic yne compound and 3.0 mL of DMF were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 10 mA for 3 hours at room temperature. The mixture was carefully quenched with 2 mL of HCl, extracted three times with ethyl acetate, dried with anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude residue was purified by rapid column chromatography using petroleum ether / ethyl acetate / acetic acid to obtain the fumaric acid derivative.
8. The method for directly synthesizing fumaric acid and succinic acid derivatives from CO2 according to claim 1, characterized in that, 0.1 mmol n Bu4NI was added to a dry 10 mL reaction tube. A C cathode and a Mg anode were installed in the reaction tube, and the tube was evacuated and filled with CO2 three times. Then, 0.2 mmol of an aromatic yne compound and 3.0 mL of CH3CN were added to the reaction mixture via syringe. The reaction mixture was electrolyzed at a constant current of 8 mA for 3 hours at room temperature. The mixture was carefully quenched with 2 mL of HCl, extracted three times with ethyl acetate, dried with anhydrous Na2SO4, and the solvent was removed under reduced pressure. The crude residue was purified by rapid column chromatography using petroleum ether / ethyl acetate / acetic acid to obtain a succinic acid derivative.