Three-component electrochemical synthesis method of dithiophosphonate

Abstract

The invention relates to the field of chemical synthesis, in particular to a three-component electrochemical synthesis method of dithiophosphonate. According to the invention, a trivalent phosphine hydrogen compound, elemental sulfur and mercaptan / phenol three-component electrochemical oxidation reaction system is constructed, and a series reaction is carried out to synthesize the phosphorus and sulfur-containing dithiophosphonate derivative in one step. The method is simple, convenient and safe in reaction operation, mild in reaction condition, simple and efficient, free of obvious by-products, relatively high in tolerance of compound functional groups, convenient in post-treatment, generally relatively high in yield, wide in substrate applicability, simple to operate and capable of avoiding the use of highly toxic thiophosphoryl chloride and foul Lawesson reagents, and can be used for large-scale synthesis.

Description

Technical Field

[0001] The invention relates to the field of chemical synthesis, in particular to a three-component electrochemical synthesis method of dithiophosphonate. Background Art

[0002] Dithiophosphonates are an important class of organic phosphorus and sulfur compounds, which are widely present in various biologically active compounds and materials. Their unique disulfide structure determines their special biological activity and chemical properties. They are widely used in medical research, biochemistry, agricultural chemistry and other fields. They can be used as alkaline esterase inhibitors, pesticides, antiviral agents, main components of lubricants, and flotation reagents for precious metal ores. At present, the main methods for synthesizing dithiophosphonate compounds and their limitations are: 1) using tetraalkane / aryl diphosphine disulfide as a phosphorus and sulfur source and synthesizing with aromatic sulfide under metal catalysis (Adv.Synth.Catal.2018,360,3488-3491), which is obtained as a by-product and has poor atom economy; 2) using tetraaryl diphosphine disulfide as a phosphorus and sulfur source and disulfide under photocatalysis (J.Org.Chem.2020,85,14708-14719), the energy conversion rate of the light source is not high; 3) obtained by the Atherton-Todd type reaction of thiodialkylphosphine and thiol / phenol (J.Sulfur Chem.2014,35,237-247), the atom utilization is low and an excess of chlorination reagent is required; 4) phosphonate obtained by dehydrogenation coupling of phosphorus oxide and thiol / phenol (Green Chem. 2015, 17, 314-319; Org. Lett. 2016, 18, 5114-5117; Tetrahedron 2017, 73, 3133-3138; Chem. Commun. 2019, 55, 4981-4984; Org. Lett. 2021, 23, 1541-1547.) is used as a raw material and reacts with a thio reagent such as Lawesson's reagent to generate the corresponding dithiophosphonate compound, but the thio reagent often has a foul odor. Recently, a multicomponent reaction developed using phosphorus pentasulfide and alkyl alcohols as raw materials has successfully achieved the synthesis of dithiophosphates (Green Chem. 2023, 25, 10678-10683; Org. Lett. 2024, 26, 3883-3888; Chin. Chem. Lett. 2024, 35, 110112; Org. Chem. Front. 2024, 11, 171-175; J. Org. Chem. 2024, 89, 10974-10986.), however, diaryl-substituted dithiophosphonates are not included.

[0003] As mentioned above, the traditional synthesis method of dithiophosphonates usually requires the use of toxic or expensive metal catalysts, the need to prepare phosphorus sulfide raw materials in advance, and the reaction conditions are relatively harsh, with cumbersome operation, low atom economy and poor functional group compatibility. The introduction of electrochemical multi-component tandem synthesis technology is expected to circumvent the above shortcomings. Diarylphosphine hydrogen has been applied to the electrochemical oxidative cross-coupling reaction of nitrogen-containing nucleophiles, but only unoxidized phosphorus (Chem. Sci. 2022, 13, 3002-3008) and phosphorus oxidized to phosphine oxide products (Chem. Eur. J. 2021, 27, 14931-14935) are obtained, and phosphorus-containing products oxidized by elemental sulfur have not been reported. Based on this, a three-component electrochemical synthesis route with mild reaction conditions, green, high efficiency, metal-free and environmentally friendly is developed to realize the dehydrogenative cross-coupling reaction of phosphine hydrogen compounds and thiols / phenols, which is expected to construct structurally diverse phosphorus- and sulfur-containing dithiophosphonates in a simple and green manner, providing convenience for obtaining such compounds. Summary of the invention

[0004] The main purpose of the present invention is to provide a three-component electrochemical synthesis method of dithiophosphonate, and apply the method to the derivatization of drug molecules.

[0005] The technical solution of the present invention is as follows:

[0006] A three-component electrochemical synthesis method of a dithiophosphonate, wherein the structure of the dithiophosphonate derivative is shown in Formula I.

[0007]

[0008] Wherein: R1 or R2 is one of C1-C6 alkyl, C1-C6 alkoxy, C6-C12 aryl, benzyl, and C2-C10 heterocyclic group;

[0009] R3 is any one of a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, a C6-C12 aryl group, a benzyl group, a C2-C8 alkenyl-containing substituent group, a C2-C8 alkynyl-containing substituent group, or a C2-C10 heterocyclic group;

[0010] It is characterized in that the synthesis method is shown in the following formula:

[0011]

[0012] In the formula, the preparation steps of compound I are:

[0013] S1. Compound II, compound III, elemental sulfur IV, electrolyte and additives are placed in an organic solvent, an anode and a cathode are installed, the reaction container is sealed and a constant direct current is passed for reaction;

[0014] S2. After compound III completely disappears, removing the organic solvent from the reaction mixture under reduced pressure;

[0015] S3. Use silica gel column chromatography to elute to obtain compound I.

[0016] The molar ratio of the compound II, the compound III and the elemental sulfur IV is II:III:IV=1.5-3.0:1.0:3.0-5.0.

[0017] The anode is an electrode made of graphite sheet, graphite rod, mesh glassy carbon, glassy carbon, graphite felt, foamed carbon, platinum sheet, platinum wire or stainless steel.

[0018] The cathode is an electrode made of graphite sheet, graphite rod, mesh glassy carbon, glassy carbon, foamed carbon, platinum sheet, nickel, iron, copper, stainless steel, aluminum, zinc, titanium or lead.

[0019] The electrolyte includes one or more of tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, tetrabutylammonium hydroxide, tetrabutylammonium iodide, tetrabutylammonium bromide, 1,3-dimethylimidazole iodide, tetraethylammonium tetrafluoroborate, tetraethylammonium iodide, tetrabutylammonium tetrafluoroborate, tetramethylammonium acetate, tetramethylammonium iodide, ammonium iodide, potassium iodide, sodium iodide, tetrabutylammonium acetate or tetraethylammonium perchlorate.

[0020] The additive includes one or two of 2,6-di-tert-butylphenol, tetramethylpiperidinium oxide, zinc iodide, hydroiodic acid, methanesulfonic acid, trifluoroethanol, hexafluoroisopropanol, acetic acid, propionic acid, n-butyric acid, isobutyric acid or pivalic acid.

[0021] The organic solvent includes any one or a combination of at least two of ethyl acetate, acetonitrile, dioxane, dichloromethane, tetrahydrofuran, dichloroethane, N,N-dimethylpropylene urea, N-methylpyrrolidone, dimethylformamide or dimethylacetamide.

[0022] The eluent used in the column chromatography is a mixture of petroleum ether and ethyl acetate, with a volume ratio of V petroleum ether:V ethyl acetate=100:1-2:1.

[0023] The beneficial effects of the present invention are as follows: (1) The present invention provides a three-component electrochemical synthesis method of dithiophosphonates, and the synthesis method of this type of compound is rarely reported.

[0024] (2) The preparation method of the present invention uses electric current as a traceless oxidant, the reaction does not require a catalyst or metal, the operation is simple and safe, the reaction steps are few, the raw materials are easily available, the reaction conditions are mild, there are no by-products, the substrate expansion range is wide, and the tolerance for compound functional groups is high. The product yield can reach 63%.

[0025] (3) The present invention can avoid the use of uncommercialized P(S)-H compounds and can also prepare such dithiophosphonate derivatives on a gram scale. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the NMR spectrum (hydrogen spectrum) of the product Ⅰ-1 obtained in the example of the present invention;

[0027] Figure 2 This is the NMR spectrum (carbon spectrum) of the product Ⅰ-1 obtained in the example of the present invention;

[0028] Figure 3 This is the NMR spectrum (hydrogen spectrum) of the product Ⅰ-2 obtained in the example of the present invention;

[0029] Figure 4 This is the NMR spectrum (carbon spectrum) of the product Ⅰ-2 obtained in the example of the present invention. DETAILED DESCRIPTION

[0030] The technical solution of the present invention is further described below with reference to the accompanying drawings and through specific embodiments:

[0031] The following are the best examples of the compounds prepared by the present invention. In all the following examples, the nuclear magnetic spectrum detection was obtained by a Bruker 500 instrument in CDCl3. The δ value is the internal standard relative value (CHCl3 calibration δ7.261H NMR and 77.1613CNMR. The high resolution mass spectrum (HRMS) was obtained by a 4G quadrupole time-of-flight (QTof) mass spectrometer.

[0032] Example 1

[0033] The reaction formula of Example 1, the specific compounds II-1, III-1, sulfur powder and the product I-1 structure are as follows. Experiments show that the preferred anode of the present invention is a graphite sheet, the preferred cathode is a platinum sheet, the preferred electrolyte is tetrabutylammonium iodide, the preferred additive is hexafluoroisopropanol (HFIP), the preferred direct current is 6 mA, the preferred organic solvent is acetonitrile (MeCN), the highest yield of the reaction product is 60%, the best raw material molar ratio is the molar ratio of compound II and compound III is II:III=2:1, wherein compound III should be an equivalent value, and the optimal concentration of the solution is 0.04M.

[0034]

[0035] The specific experimental steps are: in a 10 ml straight reaction tube, 25 mg (0.2 mmol, 1.0 equivalent) of compound III-1, 19 mg of sulfur powder (0.6 mmol, 3.0 equivalent), 74 mg of tetrabutylammonium iodide (0.2 mmol, 1.0 equivalent) and 0.5 mL of hexafluoroisopropanol are dissolved in 4.5 mL of acetonitrile, a graphite anode and a platinum cathode are installed, and the test tube is replaced with a nitrogen atmosphere, and then 74 mg (0.40 mmol, 2.0 equivalent) of compound II-1 is injected with a microinjector, and the reaction is carried out at room temperature for 24 hours under a direct current of 6 mA. After the reaction is completed, the reaction mixture is rotary evaporated under reduced pressure of a water pump to remove the solvent. The residue was subjected to column chromatography on 200-300 mesh silica gel with an eluent (volume ratio V petroleum ether: V ethyl acetate = 100:1-10:1) to obtain the compound shown in Ⅰ-1. The product was identified by nuclear magnetic resonance (hydrogen spectrum, carbon spectrum, phosphorus spectrum) and high-resolution mass spectrometry, and its characteristics are as follows:

[0036] P-tolyl diphenylphosphinodithioate.(41mg,Yield=60%,Rf=0.78(PE / EA=10:1))wasisolatedasawhitesolid;mp105–107℃.1H 13C NMR (100MHz, CDCl3) δ140.0 (d, J = 3.3Hz), 136.4 (d, J = 3.8Hz), 134.2, 133.3, 132.04 –131.7(m),129.9(d,J=2.5Hz),128.5(d,J=13.2Hz),123.1(d,J=5.6Hz),21.4; 31P NMR (162MHz, CDCl3) δ66.08; HRMS (ESI) m / z: [M+H]+Calcd for C19H17PS2341.0582; Found341.0579.

[0037] Example 2

[0038] Bisphosphonothioates were synthesized using 4-tert-butylbenzyl mercaptan as the sulfur source.

[0039]

[0040] The specific experimental steps are: in a 10 ml straight reaction tube, 36 mg (0.2 mmol, 1.0 equivalent) of compound III-2, 19 mg of sulfur powder (0.6 mmol, 3.0 equivalent), 74 mg of tetrabutylammonium iodide (0.2 mmol, 1.0 equivalent) and 0.5 mL of hexafluoroisopropanol are dissolved in 4.5 mL of acetonitrile, a graphite anode and a platinum cathode are installed, and the test tube is replaced with a nitrogen atmosphere, and then 74 mg (0.40 mmol, 2.0 equivalent) of compound II-1 is injected with a microinjector, and the reaction is carried out at room temperature for 24 hours under a direct current of 6 mA. After the reaction is completed, the reaction mixture is rotary evaporated under reduced pressure of a water pump to remove the solvent. The residue was subjected to column chromatography on 200-300 mesh silica gel with an eluent (volume ratio V petroleum ether: V ethyl acetate = 100:1-10:1) to obtain the compound shown in Ⅰ-2. The product was identified by nuclear magnetic resonance (hydrogen spectrum, carbon spectrum, phosphorus spectrum) and high-resolution mass spectrometry, and its characteristics are as follows:

[0041] 4-(Tert-butyl)benzyl diphenylphosphinodithioate.(50mg,Yield=63%,Rf=0.83(PE / EA=10:1)) was isolated as a colorless oil.1H 13C NMR(100MHz, CDCl3)δ150.4,134.5,133.8–133.4(m),131.8(d,J=3.1Hz),131.5( d,J=11.3Hz),129.0,128.5(d,J=13.3Hz),125.5,35.7–35.4(m),34.5,31.4; 31P NMR (162MHz, CDCl3) δ66.50; HRMS (ESI) m / z: [M+H]+Calcd for C23H25PS2397.1208; Found397.1207.

[0042] Compound I-1

[0043]

[0044] P-tolyl diphenylphosphinodithioate. (41 mg, Yield=60%, Rf=0.78 (PE / EA=10:1)) was isolated as a white solid; mp 105–107℃. 1H NMR (400 MHz, CDCl3) δ8.02–7.93 (m, 4H), 7.54–7.42 (m, 6H), 7.27–7.22 (m, 2H), 7.05 (d, J=8.5 Hz, 2H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl3) δ140.0 (d, J=3.3 Hz), 136.4 (d, J=3.8 Hz), 134.2, 133.3, 132.04–131.7 (m), 129.9 (d, J=2.5 Hz), 128.5 (d, J=13.2 Hz), 123.1 (d, J=5.6 Hz), 21.4; 31P NMR (162 MHz, CDCl3) δ66.08; HRMS (ESI) m / z: [M+H]+ Calcd for C19H17PS2 341.0582; Found 341.0579.

[0045] Compound I-2

[0046]

[0047] 4-(Tert-butyl)benzyl diphenylphosphinodithioate. (50 mg, Yield=63%, Rf=0.83 (PE / EA=10:1)) was isolated as a colorless oil. 1H NMR (400 MHz, CDCl3) δ7.92 (m, 4H), 7.48–7.37 (m, 6H), 7.20 (d, J=1.9 Hz, 4H), 4.18 (s, 1H), 4.15 (s, 1H), 1.29 (s, 9H); 13C NMR (100 MHz, CDCl3) δ150.4, 134.5, 133.8–133.4 (m), 131.8 (d, J=3.1 Hz), 131.5 (d, J=11.3 Hz), 129.0, 128.5 (d, J=13.3 Hz), 125.5, 35.7–35.4 (m), 34.5, 31.4; 31P NMR (162 MHz, CDCl3) δ66.50; HRMS (ESI) m / z: [M+H]+ Calcd for C23H25PS2 397.1208; Found 397.1207.

[0048] Compound I-3

[0049]

[0050] Phenyl diphenylphosphinodithioate. (38 mg, Yield=59%, Rf=0.67(PE / EA=10:1)) was isolated as a colorless oil. 1H NMR(400 MHz, CDCl3) δ8.02–7.92(m, 4H), 7.54–7.41(m, 6H), 7.38–7.30(m, 3H), 7.23(t, J=7.7 Hz, 2H); 13C NMR(100 MHz, CDCl3) δ136.5(dd, J=51.0, 29.6 Hz), 134.1, 133.3, 131.9(d, J=10.4 Hz), 129.4, 128.6(d, J=12.3 Hz), 126.8(d, J=5.6 Hz); 31P NMR(162 MHz, CDCl3) δ66.26; HRMS(ESI) m / z: [M+H]+ Calcd for C18H15PS2 327.0431; Found 327.0434.

[0051] Compound I-4

[0052]

[0053] 4-Methoxyphenyl diphenylphosphinodithioate. (43 mg, Yield=61%, Rf=0.72 (PE / EA=10:1)) was isolated as a white solid;mp 111–113℃. 1H NMR (400 MHz, CDCl3) δ 7.96 (m, 4H), 7.51–7.42 (m, 6H), 7.29–7.22 (m, 2H), 6.80–6.72 (m, 2H), 3.74 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 161.0, 138.0 (d, J=3.5 Hz), 132.2, 132.1–131.7 (m), 131.5 (t, J=6.2 Hz), 128.7–128.3 (m), 116.9 (d, J=5.5 Hz), 114.6 (d, J=2.3 Hz), 55.3; 31P NMR (162 MHz, CDCl3) δ 66.19; HRMS (ESI) m / z: [M+H]+ Calcd for C19H17OPS2 357.0531; Found 357.0531.

[0054] Compound I-5

[0055]

[0056] 3-Methoxyphenyl diphenylphosphinodithioate. (43 mg, Yield=61%, Rf=0.56 (PE / EA=10:1)) was isolated as a white solid;mp 117–118℃. 1H NMR(400 MHz, CDCl3) δ8.03–7.93 (m, 4H), 7.52–7.42 (m, 6H), 7.13 (t, J=7.9 Hz, 1H), 6.99–6.84 (m, 3H), 3.64 (s, 3H); 13C NMR(100 MHz, CDCl3) δ159.5 (d, J=2.4 Hz), 134.0, 133.2, 132.0 (d, J=3.1 Hz), 131.9 (d, J=10.9 Hz), 129.6 (d, J=2.3 Hz), 128.6 (d, J=13.2 Hz), 127.7 (d, J=5.6 Hz), 120.8 (d, J=3.7 Hz), 116.5 (d, J=2.9 Hz), 55.3; 31P NMR(162 MHz, CDCl3) δ66.15; HRMS(ESI) m / z: [M+H]+ Calcd for C19H17OPS2 357.0531; Found 357.0530.

[0057] Compound I-6

[0058]

[0059] 2-Methoxyphenyl diphenylphosphinodithioate. (38 mg, Yield=54%, Rf=0.51 (PE / EA=10:1)) was isolated as a colorless oil. 1H NMR (400 MHz, CDCl3) δ8.05–7.93 (m, 4H), 7.56–7.40 (m, 7H), 7.32 (m, 1H), 6.90 (t, J=7.8 Hz, 1H), 6.75 (d, J=8.2 Hz, 1H), 3.46 (s, 3H); 13C NMR (100 MHz, CDCl3) δ160.4 (d, J=3.5 Hz), 138.9 (d, J=4.2 Hz), 135.0, 134.2, 132.0–131.7 (m), 131.6 (d, J=2.9 Hz), 128.3 (d, J=13.3 Hz), 121.0 (d, J=2.2 Hz), 115.0 (d, J=5.6 Hz), 111.2 (d, J=2.3 Hz), 55.3; 31P NMR (162 MHz, CDCl3) δ65.82; HRMS (ESI) m / z: [M+H]+ Calcd for C19H17OPS2 357.0531; Found 357.0531.

[0060] Compound I-7

[0061]

[0062] 4-Fluorophenyl diphenylphosphinodithioate. (30 mg, Yield=43%, Rf=0.83(PE / EA=10:1)) was isolated as a light yellow oil. 1H NMR(400 MHz, CDCl3) δ8.00–7.90(m, 4H), 7.54–7.42(m, 6H), 7.35–7.28(m, 2H), 6.97–6.88(m, 2H); 13C NMR(100 MHz, CDCl3) δ165.2, 162.7, 138.6(dd, J=8.6, 3.6Hz), 132.4–131.7(m), 128.7(d, J=13.3Hz), 116.3(dd, J=22.1, 2.4Hz), 77.7–76.7(m); 31P NMR(162 MHz, CDCl3) δ66.72; 19F NMR(376 MHz, CDCl3) δ-111.4(s, 1F); HRMS(ESI) m / z: [M+H]+ Calcd for C18H14FPS2 345.0331 Found 345.0331.

[0063] Compound I-8

[0064]

[0065] 4-Chlorophenyl diphenylphosphinodithioate. (27 mg, Yield=38%, Rf=0.87(PE / EA=10:1)) was isolated as a light yellow oil. 1H NMR(400 MHz, CDCl3) δ8.02–7.93(m, 4H), 7.53–7.42(m, 6H), 7.28(m, 2H), 7.23–7.17(m, 2H); 13C NMR(100 MHz, CDCl3) δ137.6(d, J=3.7Hz), 136.3(d, J=3.6Hz), 133.7, 132.8, 132.1(d, J=3.0Hz), 131.8(d, J=11.0Hz), 129.2(d, J=2.3Hz), 128.6(d, J=13.3Hz), 125.2(d, J=5.6Hz); 31P NMR(162 MHz, CDCl3) δ66.66; HRMS(ESI) m / z: [M+H]+ Calcd for C18H14ClPS2 361.0036; Found 361.0037.

[0066] Compound I-9

[0067]

[0068] 4-Bromophenyl diphenylphosphinodithioate.(36mg,Yield=45%,Rf=0.85(PE / EA=10:1)) was isolated as a colorless oil.1H NMR (400MHz, CDCl3) δ8.01–7.91(m,4H),7.55–7.42(m,6H),7.39–7.32(m,2H),7.24–7.18(m,2H); 13C 31P NMR (162MHz, CDCl3) δ66.51; HRMS (ESI) m / z: [M+H]+Calcdfor 404.9531; Found 404.9529.

[0069] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0070] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A three-component electrochemical synthesis method of a dithiophosphonate, wherein the structure of the dithiophosphonate derivative is shown in Formula I. in: R1 or R2 is one of C1-C6 alkyl, C1-C6 alkoxy, C6-C12 aryl, benzyl, and C2-C10 heterocyclic group; R3 is any one of a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, a C6-C12 aryl group, a benzyl group, a C2-C8 alkenyl-containing substituent group, a C2-C8 alkynyl-containing substituent group, or a C2-C10 heterocyclic group; It is characterized in that the synthesis method is shown in the following formula: In formula II, the preparation steps of compound I are: S1. Compound II, compound III, elemental sulfur IV, electrolyte and additives are placed in an organic solvent, an anode and a cathode are installed, the reaction container is sealed and a constant direct current is passed for reaction; S2. After compound III completely disappears, removing the organic solvent from the reaction mixture under reduced pressure; S3. Use silica gel column chromatography to elute to obtain compound I.

2. The three-component electrochemical synthesis method of a dithiophosphonate according to claim 1, characterized in that: The molar ratio of the compound II, the compound III and the elemental sulfur IV is II:III:IV=1.5-3.0:1.0:3.0-5.

0.

3. The three-component electrochemical synthesis method of a dithiophosphonate according to claim 1, characterized in that: The anode is an electrode made of graphite sheet, graphite rod, mesh glassy carbon, glassy carbon, graphite felt, foamed carbon, platinum sheet, platinum wire or stainless steel.

4. The three-component electrochemical synthesis method of a dithiophosphonate according to claim 1, characterized in that: The cathode is an electrode made of graphite sheet, graphite rod, mesh glassy carbon, glassy carbon, foamed carbon, platinum sheet, nickel, iron, copper, stainless steel, aluminum, zinc, titanium or lead.

5. The three-component electrochemical synthesis method of a dithiophosphonate according to claim 1, characterized in that: The electrolyte includes one or more of tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, tetrabutylammonium hydroxide, tetrabutylammonium iodide, tetrabutylammonium bromide, 1,3-dimethylimidazole iodide, tetraethylammonium tetrafluoroborate, tetraethylammonium iodide, tetrabutylammonium tetrafluoroborate, tetramethylammonium acetate, tetramethylammonium iodide, ammonium iodide, potassium iodide, sodium iodide, tetrabutylammonium acetate or tetraethylammonium perchlorate.

6. The three-component electrochemical synthesis method of a dithiophosphonate according to claim 1, characterized in that: The additive includes one or two of 2,6-di-tert-butylphenol, tetramethylpiperidinium oxide, zinc iodide, hydroiodic acid, methanesulfonic acid, trifluoroethanol, hexafluoroisopropanol, acetic acid, propionic acid, n-butyric acid, isobutyric acid or pivalic acid.

7. The three-component electrochemical synthesis method of a dithiophosphonate according to claim 1, characterized in that: The organic solvent includes any one or a combination of at least two of ethyl acetate, acetonitrile, dioxane, dichloromethane, tetrahydrofuran, dichloroethane, N,N-dimethylpropylene urea, N-methylpyrrolidone, dimethylformamide or dimethylacetamide.

8. The three-component electrochemical synthesis method of a dithiophosphonate according to claim 1, characterized in that: The eluent used in the column chromatography is a mixture of petroleum ether and ethyl acetate, with a volume ratio of V petroleum ether:V ethyl acetate=100:1-2:1.

Images