Electrochemically promoted gem-diselenide reaction method of 2-indolone compounds and derivatives thereof

Abstract

The invention discloses an electrochemically promoted gem-diselenide reaction method of 2-indolone compounds and derivatives thereof, which comprises the following steps: dissolving the 2-indolone compounds and derivatives thereof and disubstituted diselenide in a solvent at room temperature in an air atmosphere, and carrying out a constant-current stirring reaction in the presence of an electrolyte to obtain a target compound. The invention provides an electrochemically promoted gem-diselenide method for 2-indolone compounds and derivatives thereof, the method is simple and easy to operate, only a small amount of solvent is used, and articles required in the method are low in toxicity, safe and environment-friendly, and can be stored at room temperature. According to the present invention, the gem-diselenide reaction of the 2-indolone compound is electrochemically promoted, the reaction activity is high, the substrate expansion range is wide, the yield is high, and the synthesized partial gem-diselenide product has good growth inhibition effect on partial plant fungi.

Description

Technical Field

[0001] This invention belongs to the field of organic compound synthesis technology, specifically relating to an electrochemically promoted method for gemsidation of 2-indolone compounds and their derivatives. Background Technology

[0002] Selenium is an essential trace element for human health and is widely found in various drugs and bioactive intermediates. In recent years, synthetic strategies for selenium-containing compounds have attracted considerable attention. For example, monoselenochemical reactions of various heterocyclic compounds with diselenyl ethers have been reported. However, these methods rely on harsh conditions such as transition metal catalysts or oxidants to achieve monoselenochemical reactions, and cannot yield gemsidated products through two consecutive selenization processes in a one-pot process. The reported methods have low atom utilization of selenium and can only produce monoselenochemical products. Therefore, developing a sustainable, catalyst-free, and green one-pot process for gemsidochemical selenization is highly desirable.

[0003] In recent years, electrochemical synthesis technology has become increasingly sophisticated, and it can cleverly utilize the redox reactions of electrons to promote the occurrence of reactions. This provides a green, stable, and sustainable route for synthesizing complex molecules using electric current to promote chemical reactions, which aligns with the concept of modern green chemistry. Prior to this, a method for the gemsidation reaction of 2-indolone compounds and their derivatives under electrochemical conditions had not been invented.

[0004] Here, we have invented a direct, catalyst-free, and additive-free electrochemically promoted gemsidation reaction method for 2-indolone compounds and their derivatives. This reaction method can achieve gemsidation reactions of various 2-indolone compounds and their derivatives with high atomic conversion efficiency, high regiodispersity, and high selectivity under mild reaction conditions. Furthermore, we have explored and found that some of the synthesized gemsidated products have good antibacterial effects, effectively inhibiting the growth of plant fungi such as *Gynostemma pentaphyllum*, *Pseudomonas aeruginosa*, and *Pseudomonas macrantha*. Finally, the electrochemical synthesis of the gemsidates and their antibacterial activity shown in this invention have not been disclosed in the prior art. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] One objective of this invention is to provide an electrochemically promoted gemdiselenlation method for 2-indolone compounds and their derivatives, which is a direct, catalyst-free, and additive-free electrochemically promoted gemdiselenlation strategy for 2-indolone compounds and their derivatives.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: an electrochemically promoted method for gemsidation reaction of 2-indolone compounds and their derivatives, comprising,

[0009] The 2-indolone compounds and their derivatives shown in Formula I and the diselenide compounds shown in Formula II were dissolved in a solvent at room temperature and in an air atmosphere, and the reaction was carried out under constant current stirring in the presence of an electrolyte to obtain the target compound shown in Formula III.

[0010]

[0011] R 3 -Se-Se-R 3 (Formula II);

[0012]

[0013] Among them, R 1 It is selected from one of methyl, methoxy, pinacol borate, halogen, trifluoromethyl, cyano, nitro, and methyl formate.

[0014] R 2 Selected from one of hydrogen, methyl, and phenyl;

[0015] R 3 It is selected from one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-halophenyl, 4-trifluorotolyl, 2-thienyl, 2-naphthyl, methyl, ethyl, and benzyl.

[0016] As a preferred embodiment of the electrochemically promoted gemiselenlation reaction method for 2-indolone compounds and their derivatives of the present invention, wherein the molar ratio of the 2-indolone compounds and their derivatives to the diselenide compounds is 1:1.2.

[0017] As a preferred embodiment of the electrochemically promoted gemine diselenlation reaction method for 2-indolone compounds and their derivatives of the present invention, wherein: the 2-indolone compounds and their derivatives are 2-indolone, 5-methyl-2-indolone, 5-methoxy-2-indolone, 5-boronate pinacol ester-2-indolone, 6-methyl-2-indolone, 6-fluoro-2-indolone, 6-chloro-2-indolone, 6-bromo-2-indolone, 5-fluoro-2-indolone, 5- One of the following: chloro-2-indolone, 5-nitro-2-indolone, 6-trifluoromethyl-2-indolone, 6-cyano-2-indolone, methyl 6-carboxylate-2-indolone, N-methyl-2-indolone, N-phenyl-2-indolone, 7-aza-2-indolone, 2-benzofuranone, N-acetyl-3-indolone, and 5-(2-(4-(1,2-benzisothiazol-3-yl)-1-piperazinyl)ethyl)-6-chloro-2-indolone.

[0018] As a preferred embodiment of the electrochemically promoted gemiselylation reaction method for 2-indolone compounds and their derivatives of the present invention, wherein the diselenide compound is one of diphenyl diselenide, bis(4-methylphenyl)diselenide, bis(4-methoxyphenyl)diselenide, bis(4-fluorophenyl)diselenide, bis(4-chlorophenyl)diselenide, bis(4-trifluoromethylphenyl), bis(2,2'-thienyl)diselenide, bis(2,2'-naphthyl)diselenide, dimethyldiselenide, diethyldiselenide, and dibenzyldiselenide.

[0019] As a preferred embodiment of the electrochemically promoted gemisenylation reaction method for 2-indolone compounds and their derivatives of the present invention, the solvent is one of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, and tetrahydrofuran.

[0020] As a preferred embodiment of the electrochemically promoted gemiselation reaction method for 2-indolone compounds and their derivatives of the present invention, wherein: the electrolyte is one of tetrabutylammonium iodide, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium bromide, tetramethylammonium iodide, and ammonium iodide; and the molar ratio of the electrolyte to the 2-indolone compound and its derivatives represented by Formula I is 1:1.

[0021] As a preferred embodiment of the electrochemically promoted gemiselylation reaction method for 2-indolone compounds and their derivatives of the present invention, wherein: in the electrode used for the constant current stirring reaction, the cathode is an electrode material containing carbon, platinum, and nickel, and the anode is an electrode material containing carbon and platinum.

[0022] As a preferred embodiment of the electrochemically promoted gemiselenlation reaction method for 2-indolone compounds and their derivatives of the present invention, the constant current reaction is 5-15 mA and the reaction time is 1-2 hours.

[0023] Another object of the present invention is to provide gemdiselenated products obtained by the electrochemically promoted gemdiselenation reaction method of 2-indolone compounds and their derivatives as described above.

[0024] Another object of the present invention is to provide the application of the gemsidated products as described above in inhibiting the growth of plant fungi, said plant fungi including one or more of grape rot fungi, stone fruit rot fungi, and apple ring rot fungi.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The electrical energy required by this invention is readily available, environmentally friendly, and inexpensive. The process is simple and easy to operate, using only a small amount of solvent. The reagents used in the method are safe, environmentally friendly, and can be stored at room temperature. This invention provides an electrochemically promoted method for the gemsidation of 2-indolone compounds and their derivatives. This method exhibits high reactivity, high regioselectivity, a broad substrate scope, and high yield. Furthermore, the synthesized gemsidated products have good antibacterial effects and can be applied to inhibit the growth of some plant fungi. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0028] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 2 of this invention;

[0029] Figure 2 The nuclear magnetic resonance carbon spectrum of the product prepared in Example 2 of this invention;

[0030] Figure 3 The figures show the experimental results of the products prepared in Examples 1 and 13 of this invention inhibiting the growth of grape seed rot fungi.

[0031] Figure 4 The figures show the experimental results of the products prepared in Examples 1 and 13 of this invention inhibiting the growth of the brown rot fungus in stone fruits.

[0032] Figure 5 The figures show the experimental results of the products prepared in Examples 1 and 13 of this invention inhibiting the growth of apple ring rot fungus. Detailed Implementation

[0033] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0034] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0035] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0036] Unless otherwise specified, the following are the references used in the examples: 2-indolone, 5-methyl-2-indolone, 5-methoxy-2-indolone, 5-boronate pinacol ester-2-indolone, 6-methyl-2-indolone, 6-fluoro-2-indolone, 6-chloro-2-indolone, 6-bromo-2-indolone, 5-fluoro-2-indolone, 5-chloro-2-indolone, 5-nitro-2-indolone, 6-trifluoromethyl-2-indolone, and 6-cyano-2-indolone. The raw materials for doleone, methyl 6-carboxylate-2-indolone, N-methyl-2-indolone, N-phenyl-2-indolone, 7-aza-2-indolone, 2-benzofuranone, N-acetyl-3-indolone, 5-(2-(4-(1,2-benzisothiazol-3-yl)-1-piperazinyl)ethyl)-6-chloro-2-indolone, diphenyldiselenoether, dimethyldiselenoether, diethyldiselenoether, and dibenzyldiselenoether were all purchased directly from commercial sources. In addition, the raw materials bis(4-methylphenyl)diselenoether, bis(4-methoxyphenyl)diselenoether, bis(4-fluorophenyl)diselenoether, bis(4-chlorophenyl)diselenoether, bis(4-trifluoromethylphenyl), bis(2,2'-thienyl)diselenoether and bis(2,2'-naphthyl)diselenoether were all prepared by referring to the methods disclosed in the literature (Org. Lett., 2010, 12, 3288-3291).

[0037] The electrochemical reaction apparatus and operation method used in the example are as follows: First, add 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 2-indolone, and 0.24 mmol of diphenyldiselenes to the reaction flask in sequence, and then add 5 mL of acetonitrile (CH3CN) as a solvent. Insert two fixed stone felt electrode rods into the reaction flask so that 2 / 3 of the two stone felt electrode rods are immersed in the solution. Then connect the two electrode rods to the positive and negative terminals of the power supply respectively, turn on the power supply, adjust the current to 10 mA, and turn off the power supply after the reaction is completed.

[0038] Example 1

[0039] The electrochemically promoted reaction of 2-indolone with diphenyldiselenes proceeds as follows:

[0040] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 71%.

[0041] The product was characterized, and the results are as follows: 1 H NMR(500MHz, CDCl3)δ8.15(s,1H),7.46-7.40(m,4H),7.30-7.26(m,2H),7.14(t,J =7.7Hz,4H),7.02(td,J=7.5,1.7Hz,1H),6.90–6.83(m,2H),6.55(d,J=7.8Hz,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.36,139.53,137.25,129.72,129.60,128.87,128.80,127.33,126.15,122.38,109.73,46.76.

[0042] The product structural formula is:

[0043]

[0044] Example 2

[0045] Based on Example 1, the reaction conditions were optimized, and the optimization results are shown in Table 1.

[0046] Table 1

[0047]

[0048] *Note: In this embodiment, "yield" refers to the final separation yield.

[0049] The results of the above optimization conditions show that, under the same reaction conditions, changing the cathode or anode material will lead to a decrease in yield. Using GF as both anode and cathode can achieve a good final separation yield of 71% for the target product.

[0050] Under the same reaction conditions, the yield decreases as the constant current increases (from 10 mA to 15 mA), and the yield also decreases as the constant current decreases (from 10 mA to 5 mA). Therefore, a constant current of 10 mA is the optimal reaction current.

[0051] Under the same reaction conditions, the target product can be obtained by using other electrolytes, such as tetramethylammonium iodide, tetrabutylammonium bromide, and ammonium iodide. The reaction will not occur if the electrolyte tetrabutylammonium iodide is not added. Therefore, the reaction yield is optimal when tetrabutylammonium iodide is used as the electrolyte.

[0052] Under the same reaction conditions, the effect of the solvent on the reaction was studied, and it was found that using acetonitrile as the solvent yielded the optimal product. Changing the solvent type, such as to N,N-dimethylformamide or dimethyl sulfoxide, decreased the yield, while replacing the solvent with dichloromethane or tetrahydrofuran prevented the reaction from occurring. Therefore, using acetonitrile as the solvent allows for achieving a more ideal yield.

[0053] Under the same reaction conditions, a longer reaction time is not necessarily better; a reaction time of 1 hour yields the highest yield.

[0054] Under the same reaction conditions, the target product cannot be obtained without the application of electricity.

[0055] Example 3

[0056] The electrochemically promoted reaction of 5-methyl-2-indolone with diphenyldiselenoether proceeds as follows:

[0057] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 5-methyl-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 74%.

[0058] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.96 (s, 1H), 7.42 (d, J = 7.6Hz, 4H), 7.28 (t, J = 7.4Hz, 2H), 7.14 (t ,J=7.6Hz,4H),6.83(d,J=7.9Hz,1H),6.55(s,1H),6.51(d,J=7.9Hz,1H),2.16(s,3H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.93,137.25,137.13,131.63,129.47,129.37,129.22,128.69,127.56,126.58,109.73,47.12,21.02.

[0059] The product structural formula is:

[0060]

[0061] Example 4

[0062] The electrochemically promoted reaction of 5-methoxy-2-indolone with diphenyldiselenoether proceeds as follows:

[0063] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 5-methoxy-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 82%.

[0064] The product was characterized, and the results are as follows: 1 H NMR(500MHz, CDCl3)δ9.03(s,1H),7.46–7.42(m,4H),7.30–7.26(m,2H),7.15(t,J=7.7Hz, 4H),6.58(dd,J=8.5,2.6Hz,1H),6.53(d,J=8.5Hz,1H),6.35(d,J=2.6Hz,1H),3.58(s,3H). 13 C{ 1H}NMR (126MHz, CDCl3) δ176.88,154.39,136.09,132.11,129.51,128.53,127.77,126.40,114.20,110.38,109.64,54.72,46.32.

[0065] The product structural formula is:

[0066]

[0067] Example 5

[0068] The electrochemically promoted reaction of 5-boronate pinacol ester-2-indolone with diphenyldiselenoether proceeds as follows:

[0069] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of pinacol 5-borate-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 75%.

[0070] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ9.07 (s, 1H), 7.55 (d, J = 7.5Hz, 1H), 7.45–7.39 (m, 5H), 7. 28(t,J=7.6Hz,2H),7.14(t,J=7.6Hz,4H),6.64(d,J=7.5Hz,1H),1.37(s,12H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ176.87,141.25,136.06,134.93,131.31,128.50,127.89,127.70,126.21,108.33,82.65,45.29,23.89.

[0071] The product structural formula is:

[0072]

[0073] Example 6

[0074] The electrochemically promoted reaction of 6-methyl-2-indolone with diphenyldiselenoether proceeds as follows:

[0075] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 6-methyl-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 64%.

[0076] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.75(s,1H),7.44(d,J=7.6Hz,4H),7.28(t,J=7.6Hz,2H),7.14(t ,J=7.6Hz,4H),6.71(d,J=7.7Hz,1H),6.65(d,J=7.7Hz,1H),6.45(s,1H),2.24(s,3H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ178.04,139.68,139.26,137.16,129.48,128.75,127.53,126.59,125.62,123.02,110.80,46.97,21.74.

[0077] The product structural formula is:

[0078]

[0079] Example 7

[0080] The electrochemically promoted reaction of 6-fluoro-2-indolone with diphenyldiselenoether proceeds as follows:

[0081] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 6-fluoro-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 72%.

[0082] The product was characterized, and the results are as follows: 1H NMR(500MHz, CDCl3)δ8.75(s,1H),7.42(dd,J=7.5,1.5Hz,4H),7.30(td,J=7.5,1.5Hz,2H),7.1 6(t,J=7.5Hz,4H),6.77(dd,J=8.5,5.5Hz,1H),6.56-6.51(m,1H),6.35(dd,J=8.5,2.5Hz,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ178.10,163.93,161.97,140.84,140.75,137.23,137.20,129.78 ,128.92,127.33,127.25,127.20,125.21,125.18,109.06,108.88,98.53,98.31,46.05. 19 FNMR (471MHz, CDCl3) δ-110.12 (td, J = 9.1, 5.1Hz).

[0083] The product structural formula is:

[0084]

[0085] Example 8

[0086] The electrochemically promoted reaction of 6-chloro-2-indolone with diphenyldiselenoether proceeds as follows:

[0087] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 6-chloro-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 67%.

[0088] The product was characterized, and the results are as follows: 1 H NMR(500MHz, CDCl3)δ8.96(s,1H),7.42(dd,J=7.9,1.4Hz,4H),7.33–7.28(m,2H),7.17(t ,J=7.9Hz,4H),6.83(dd,J=8.1,1.9Hz,1H),6.73(d,J=8.1Hz,1H),6.64(d,J=1.9Hz,1H). 13 C{1 H}NMR (126MHz, CDCl3) δ177.90,140.55,137.20,134.43,129.84,128.96,128.20,127.09,126.78,122.39,110.65,46.09.

[0089] The product structural formula is:

[0090]

[0091] Example 9

[0092] The electrochemically promoted reaction of 6-bromo-2-indolone with diphenyldiselenoether proceeds as follows:

[0093] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 6-chloro-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 59%.

[0094] The product was characterized, and the results are as follows: 1 H NMR(500MHz, CDCl3)δ8.95(s,1H),7.44–7.40(m,4H),7.33–7.29(m,2H),7.17(t,J=7 .6Hz, 4H), 6.99 (dd, J=8.1, 1.8Hz, 1H), 6.79 (d, J=1.8Hz, 1H), 6.68 (d, J=8.1Hz, 1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.76,140.68,137.22,137.19,129.86,129.00,128.97,127.06,125.29,122.32,113.47,46.15.

[0095] The product structural formula is:

[0096]

[0097] Example 10

[0098] The electrochemically promoted reaction of 5-fluoro-2-indolone with diphenyldiselenoether proceeds as follows:

[0099] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 5-fluoro-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 61%.

[0100] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.50(s,1H),7.46–7.41(m,4H),7.33–7.28(m,2H),7.17(t,J=7.6Hz,4H),6.73(td,J=8.8,2.6Hz,1H),6.54–6.48(m,2H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.75,159.73,157.81,137.25,135.45,131.48,131.42, 129.87,128.97,127.00,115.49,115.30,113.65,113.44,110.47,110.41,46.63. 19 F NMR (471MHz, CDCl3) δ-120.19 (td, J = 8.7, 4.2Hz).

[0101] The product structural formula is:

[0102]

[0103] Example 11

[0104] The electrochemically promoted reaction of 5-chloro-2-indolone with diphenyldiselenes proceeds as follows:

[0105] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 5-chloro-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 53%.

[0106] The product was characterized, and the results are as follows: 1 H NMR(500MHz, CDCl3)δ8.53(s,1H),7.43(dd,J=8.0,1.5Hz,4H),7.31(td,J=8.0,1.5Hz,2H), 7.21–7.16(m,4H),6.99(dt,J=8.2,2.0Hz,1H),6.68(d,J=2.0Hz,1H),6.51(d,J=8.2Hz,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.36,137.90,137.31,131.40,129.93,128.99,128.71,127.67,126.99,126.31,110.75,46.22.

[0107] The product structural formula is:

[0108]

[0109] Example 12

[0110] The electrochemically promoted reaction of 5-nitro-2-indolone with diphenyldiselenes proceeds as follows:

[0111] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 5-nitro-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 79%.

[0112] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ9.46 (s, 1H), 8.00 (dd, J = 8.6, 2.3Hz, 1H), 7.52 (d, J = 2.3Hz, 1H) ,7.45–7.40(m,4H),7.35–7.30(m,2H),7.17(t,J=7.8Hz,4H),6.78(d,J=8.6Hz,1H). 13 C{ 1H}NMR (126MHz, CDCl3) δ178.55,145.03,143.12,137.25,130.66,130.31,129.21,126.59,125.49,121.79,109.99,45.38.

[0113] The product structural formula is:

[0114]

[0115] Example 13

[0116] The electrochemically promoted reaction of 6-trifluoromethyl-2-indolone with diphenyldiselenes is as follows:

[0117] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 6-trifluoromethyl-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 83%.

[0118] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.89(s,1H),7.42(dd,J=8.0,1.4Hz,4H),7.33–7.28(m,2H),7.19–7.11(m,5H),6.94(d,J=7.9Hz,1H),6.84(s,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.82,139.95,137.22,133.77,131.32,131.06,130.80,130.01, 129.01,126.79,126.12,124.81,122.64,119.34,119.31,107.04,107.01,106.98,45.85. 19 F NMR(471MHz, CDCl3)δ-62.55(s).

[0119] The product structural formula is:

[0120]

[0121] Example 14

[0122] The electrochemically promoted reaction of 6-cyanomethyl-2-indolone with diphenyldiselenoether proceeds as follows:

[0123] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 6-cyano-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 82%.

[0124] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ9.02 (s, 1H), 7.40 (d, J = 7.3Hz, 4H), 7.31 (t, J = 7.4Hz, 2H), 7.19–7.14 (m, 5H), 6.89 (d, J = 7.8Hz, 1H), 6.86 (s, 1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.20,140.15,137.20,135.17,130.16,129.12,126.60,126.59,126.50,118.43,112.79,111.93,45.62.

[0125] The product structural formula is:

[0126]

[0127] Example 15

[0128] The electrochemically promoted reaction of methyl 6-carboxylate-2-indolone with diphenyldiselenes is as follows:

[0129] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of methyl 6-carboxylate-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 78%.

[0130] The product was characterized, and the results are as follows:1 H NMR (500MHz, CDCl3) δ9.07 (s, 1H), 7.57 (dd, J = 8.0, 1.5Hz, 1H), 7.40 (d, J = 7.6Hz, 4H),7.30–7.25(m,3H),7.13(t,J=7.6Hz,4H),6.90(d,J=8.0Hz,1H),3.87(s,3H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.60,166.48,139.77,137.16,134.93,130.44,129.89,128.97,126.85,125.72,123.99,110.78,52.32,46.27.

[0131] The product structural formula is:

[0132]

[0133] Example 16

[0134] The electrochemically promoted reaction of N-methyl-2-indolone with diphenyldiselenes proceeds as follows:

[0135] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of N-methyl-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 72%.

[0136] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ7.42–7.37(m,4H),7.29–7.24(m,2H),7.13(t,J=7.6Hz,4H), 7.04(td,J=7.6,1.5Hz,1H),6.92–6.84(m,2H),6.37(d,J=7.8Hz,1H),2.81(s,3H). 13 C{ 1H}NMR (126MHz, CDCl3) δ175.11,142.14,137.31,129.46,129.36,128.77,128.55,127.12,125.76,122.34,107.68,46.25,26.32.

[0137] The product structural formula is:

[0138]

[0139] Example 17

[0140] The electrochemically promoted reaction of N-phenyl-2-indolone with diphenyldiselenes proceeds as follows:

[0141] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of N-phenyl-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 75%.

[0142] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ7.46(d,J=7.4Hz,4H),7.36(t,J=7.4Hz,2H),7.31(td,J=6.0,2.3Hz,3H),7.22( dd,J=6.0,2.3Hz,1H),7.17(t,J=7.4Hz,4H),7.00–6.96(m,2H),6.76–6.72(m,2H),6.31–6.26(m,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ174.24,142.49,137.50,134.13,129.64,129.60,129 .42,128.74,128.71,128.08,127.02,126.44,126.20,122.89,108.90,46.55.

[0143] The product structural formula is:

[0144]

[0145] Example 18

[0146] The electrochemically promoted reaction of 7-aza-2-indolone with diphenyldiselenoether proceeds as follows:

[0147] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 7-aza-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 79%.

[0148] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ10.14(s,1H),7.90(dd,J=7.3,1.6Hz,1H),7.44(dd,J=7.9,1.5Hz,4H),7. 31–7.26(m,2H),7.16(t,J=7.9Hz,4H),6.81(dd,J=7.5,1.6Hz,1H),6.69(dd,J=7.5,1.6Hz,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ175.95,154.52,146.63,137.29,133.48,129.86,128.92,126.98,124.59,117.68,45.60.

[0149] The product structural formula is:

[0150]

[0151] Example 19

[0152] The electrochemically promoted reaction of 2-benzofuranone with diphenyldiselenoether proceeds as follows:

[0153] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of 2-benzofuranone, 0.24 mmol of diphenyldiselenoether, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 68%.

[0154] The product was characterized, and the results are as follows:1 H NMR (500MHz, CDCl3) δ7.46–7.42(m,4H),7.34–7.30(m,2H),7.18(t,J=7.6Hz,4H),7.09 (td,J=7.7,1.7Hz,1H),7.06–7.03(m,1H),7.00(t,J=7.5Hz,1H),6.70(d,J=8.0Hz,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ174.91,151.80,137.32,130.07,129.73,129.07,128.10,126.78,125.74,124.14,110.44,42.18.

[0155] The product structural formula is:

[0156]

[0157] Example 20

[0158] The electrochemically promoted reaction of N-acetyl-3-indolone with diphenyldiselenes proceeds as follows:

[0159] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 0.2 mmol of N-acetyl-3-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 61%.

[0160] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.08(d,J=8.6Hz,1H),7.41–7.32(m,6H),7.17(t,J=7.5Hz,2H),7.05(t,J=7.6Hz,4H),6.91(t,J=7.5Hz,1H),3.08(s,3H). 13 C{ 1H}NMR (126MHz, CDCl3) δ194.27,170.71,151.90,137.02,136.76,131.60,130 .02,129.26,129.07,125.74,124.13,123.71,122.69,117.81,66.77,27.22.

[0161] The product structural formula is:

[0162]

[0163] Example 21

[0164] The electrochemically promoted reaction of 5-(2-(4-(1,2-benzisothiazol-3-yl)-1-piperazinyl)ethyl)-6-chloro-2-indolone with diphenyldiselenes is as follows:

[0165] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 5-(2-(4-(1,2-benzisothiazol-3-yl)-1-piperazinyl)ethyl)-6-chloro-2-indolone, 0.24 mmol of diphenyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (2:1) as eluents. The final yield was 28%.

[0166] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.46 (s, 1H), 7.93 (d, J = 8.2Hz, 1H), 7.82 (d, J = 8.1Hz, 1H), 7.50–7.43 (m, 5H), 7.37 (t, J = 7.6Hz, 1H), 7.33–7. 29(m,2H),7.18(t,J=7.6Hz,4H),6.62(s,1H),6.57(s,1H),3.62(t,J=4.7Hz,4H),2.81–2.74(m,6H),2.49(dd,J=9.6,6.3Hz,2H). 13 C{ 1H}NMR (126MHz, CDCl3) δ177.18,163.88,152.89,138.54,137.33,133.81,128.96,128.44,1 28.16,128.11,127.65,127.39,123.99,120.70,110.76,58.45,52.94,50.08,46.17,30.34.

[0167] The product structural formula is:

[0168]

[0169] Example 22

[0170] The electrochemically promoted reaction of 2-indolone with bis(4-methylphenyl)diselelenide proceeds as follows:

[0171] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of bis(4-methylphenyl)diselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (5:4) as eluents. The final separation yield was 67%.

[0172] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ7.76 (s, 1H), 7.31 (d, J = 8.4Hz, 4H), 7.03 (td, J = 7.7, 1.5Hz, 1H),6.95(d,J=7.5Hz,5H),6.90–6.86(m,1H),6.54(d,J=7.7Hz,1H),2.27(s,6H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.73,139.76,139.59,137.21,130.01,129.62,128.71,126.01,123.82,122.28,109.88,46.65,21.39.

[0173] The product structural formula is:

[0174]

[0175] Example 23

[0176] The electrochemically promoted reaction of 2-indolone with bis(4-methylphenyl)diselelenide proceeds as follows:

[0177] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of bis(4-methylphenyl)diselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (7:5) as eluents. The final separation yield was 73%.

[0178] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.35 (s, 1H), 7.38–7.31 (m, 4H), 7.07–7.00 (m, 1H), 6.92 (d, J = 7. 3Hz,1H),6.89(d,J=7.3Hz,1H),6.70–6.62(m,4H),6.57(d,J=7.8Hz,1H),3.73(s,3H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.58,160.83,139.55,138.99,130.02,128.70,126.07,122.30,117.95,114.37,109.77,55.25,46.86.

[0179] The product structural formula is:

[0180]

[0181] Example 24

[0182] The electrochemically promoted reaction of 2-indolone with bis(4-fluorophenyl)diselelenide proceeds as follows:

[0183] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of bis(4-methylphenyl)diselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 71%.

[0184] The product was characterized, and the results are as follows:1 H NMR (500MHz, CDCl3) δ8.80(s,1H),7.40(dd,J=8.7,5.6Hz,4H),7.09–7.05(m,1H),6.91(d,J=7.8Hz,2H),6.83(t,J=8.7Hz,4H),6.63(d,J=7.8Hz,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ177.55,164.83,162.84,139.57,139.49,139.42,129 .25,129.22,125.91,122.57,121.97,121.95,116.20,116.03,110.09,46.90. 19 F NMR(471MHz, CDCl3)δ-110.29–-110.38(m).

[0185] The product structural formula is:

[0186]

[0187] Example 25

[0188] The electrochemically promoted reaction of 2-indolone with bis(4-chlorophenyl)diselenes is as follows:

[0189] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of bis(4-methylphenyl)diselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 65%.

[0190] The product was characterized, and the results are as follows: 1 H NMR(500MHz, CDCl3)δ8.13(s,1H),7.35(d,J=8.3Hz,4H),7.15–7.11(m,4H),7.11 –7.08(m,1H),6.99(d,J=7.5Hz,1H),6.93(t,J=7.5Hz,1H),6.61(d,J=7.6Hz,1H). 13 C{ 1H}NMR (126MHz, CDCl3) δ176.74,139.42,138.56,136.41,129.39,129.20,129.13,125.98,125.20,122.73,110.02,46.72.

[0191] The product structural formula is:

[0192]

[0193] Example 26

[0194] The electrochemically promoted reaction of 2-indolone with bis(4-trifluoromethylphenyl)diselenoether proceeds as follows:

[0195] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of bis(4-trifluoromethylphenyl)diselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 52%.

[0196] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.25(s,1H),7.56(d,J=8.0Hz,4H),7.41(d,J=8.0Hz,4H),7.11(td ,J=7.8,1.4Hz,1H),7.00(d,J=7.8Hz,1H),6.93(t,J=7.8Hz,1H),6.62(d,J=7.8Hz,1H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ176.86,139.40,137.87,137.19,132.22,131.51,129 .76,128.62,125.83,125.67,125.64,125.61,125.58,122.94,110.30,46.83. 19 F NMR(471MHz, CDCl3)δ-62.85(s).

[0197] The product structural formula is:

[0198]

[0199] Example 27

[0200] The electrochemically promoted reaction of 2-indolone with bis(2,2'-thienyl)diselenes is as follows:

[0201] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of bis(2,2'-thienyl)diselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 76%.

[0202] The product was characterized, and the results are as follows: 1 H NMR(500MHz,DMSO-d6)δ10.61(s,1H),7.72–7.67(m,2H),7.11–7.07(m,3H),7.01(dd, J=5.3,3.5Hz,2H),6.80(t,J=7.6Hz,1H),6.62(d,J=7.6Hz,1H),6.52(d,J=7.6Hz,1H). 13 C{ 1 H}NMR(126MHz,DMSO-d6)δ175.53,141.47,139.29,134.84,130.02,128.76,128.22,125.60,122.01,121.47,110.18,50.38.

[0203] The product structural formula is:

[0204]

[0205] Example 28

[0206] The electrochemically promoted reaction of 2-indolone with bis(2,2'-naphthyl)diselenes is as follows:

[0207] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of bis(2,2'-naphthyl)diselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final yield was 61%.

[0208] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ8.27(s,1H),7.94(s,2H),7.73(d,J=7.9Hz,2H),7.64(d,J=8.0Hz,2H),7.58(d,J=8.5Hz,2H),7.48(d,J=7.6Hz, 1H),7.47–7.45(m,2H),7.45–7.40(m,3H),7.02(d,J=7.6Hz,1H),6.96(t,J=7.7Hz,1H),6.84(t,J=7.6Hz,1H),6.39(d,J=7.7Hz,1H). 13 C{ 1 H}NMR(126MHz,CDCl3)δ177.23,139.53,137.40,133.41,133.35,129.78,128 .98,128.13,127.71,127.11,126.37,126.13,124.72,122.43,109.88,46.92.

[0209] The product structural formula is:

[0210]

[0211] Example 29

[0212] The electrochemically promoted reaction of 2-indolone with dimethyl diselenoether proceeds as follows:

[0213] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of dimethyl diselenoether, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution, and then the solution was distilled with petroleum ether and ethyl acetate.

[0214] (3:2) was used as the eluent, and silica gel column chromatography was used for separation, with a final separation yield of 74%.

[0215] The product was characterized, and the results are as follows: 1 H NMR(500MHz, CDCl3) δ9.40(s,1H),7.37(dd,J=7.6,1.2Hz,1H),7.23(td,J=7.7,1 .3Hz,1H),7.08(td,J=7.6,1.0Hz,1H),6.96(dt,J=7.7,1.0Hz,1H),2.11(s,6H). 13C{ 1 H}NMR (126MHz, CDCl3) δ178.36,139.38,130.41,129.20,124.96,123.14,110.45,38.55,6.45.

[0216] The product structural formula is:

[0217]

[0218] Example 30

[0219] The electrochemically promoted reaction of 2-indolone with diethyldiselenes proceeds as follows:

[0220] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of diethyldiselenes, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and the solution was then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 70%.

[0221] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ9.40 (s, 1H), 7.40 (d, J = 7.4Hz, 1H), 7.24–7.19 (m, 1H), 7.1 0–7.05(m,1H),6.95(d,J=7.4Hz,1H),2.79–2.67(m,4H),1.26(t,J=7.6Hz,6H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ179.32,139.23,130.91,129.08,125.21,123.12,110.51,39.07,20.62,14.73.

[0222] The product structural formula is:

[0223]

[0224] Example 31

[0225] The electrochemically promoted reaction of 2-indolone with dibenzyldiselenes proceeds as follows:

[0226] Under air atmosphere, 0.1 mmol of tetrabutylammonium iodide (Bu4NI), 2-indolone, 0.24 mmol of dibenzyl diselenide, and 5 mL of acetonitrile (CH3CN) were added sequentially to a reaction flask. The mixture was stirred at a constant current of 10 mA at 25 °C for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC) during stirring. After the reaction was complete, the solvent was removed by vacuum distillation of the reaction solution under vacuum, and then separated by silica gel column chromatography using petroleum ether and ethyl acetate (3:2) as eluents. The final separation yield was 68%.

[0227] The product was characterized, and the results are as follows: 1 H NMR (500MHz, CDCl3) δ9.34 (s, 1H), 7.40 (d, J = 7.6Hz, 1H), 7.26–7.22 (m, 1H), 7. 19(s,10H),7.08(t,J=7.6Hz,1H),6.95(d,J=7.6Hz,1H),4.05(d,J=1.9Hz,4H). 13 C{ 1 H}NMR (126MHz, CDCl3) δ178.29,139.54,136.65,129.80,129.32,129.06,128.52,127.15,125.11,123.18,110.66,41.48,30.73.

[0228] The product structural formula is:

[0229]

[0230] Example 32

[0231] The gem-selenized products synthesized in Examples 1 and 13 were used to test the growth activity of *Gynostemma pentaphyllum*, *Pseudomonas erythropus*, and *Pseudomonas macrantha*.

[0232] The experimental method for activity testing was as follows: First, using dimethyl sulfoxide (DMSO) as a solvent, the test solution prepared in Example 1 was prepared to a concentration of 10 mg / mL. Then, 0.5 mL of the test solution was added dropwise to the prepared PDA culture medium. Before it cooled and solidified, it was poured evenly into a petri dish to obtain PDA culture medium containing the test solution. Using the same method, a control group culture medium containing only DMSO was obtained. Then, using a 6 mm diameter sterile punch, mycelial cakes were punched from the edge of the previously cultured colonies and placed in the center of both the PDA plate containing the test solution and the control group PDA plate. The plates were incubated at 30°C under darkness for 15 days. Each compound was repeated three times, and colony growth was observed and recorded.

[0233] The experimental test results are shown below. Figure 3 ,4 As shown in Figure 5.

[0234] The antibacterial rate was calculated:

[0235] Inhibition rate (%) = {control mycelial diameter (mm) - treated mycelial diameter (mm)} / {control mycelial diameter (mm) - 0.6mm} × 100%;

[0236] The antibacterial rate results are shown in Table 2:

[0237] Table 2

[0238] Grape cavitation bacteria Brown rot fungus of stone fruit Apple ring rot fungus Example 1 98 100 100 Example 13 92 100 100

[0239] The data in Table 2 show that the compound has good inhibitory activity against plant pathogenic fungi such as *Botrytis cinerea*, *Pythium strumarium*, and *Pseudomonas aeruginosa*.

[0240] This invention provides an electrochemically promoted gemdiselenlation method for 2-indolone compounds and their derivatives. The method is simple and easy to operate, uses only a small amount of solvent, and the required materials are of low toxicity, making it safe and environmentally friendly, and it can be stored at room temperature. This electrochemically promoted gemdiselenlation reaction of 2-indolone compounds exhibits high reactivity, a broad substrate scope, and high yield.

[0241] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for electrochemically promoted gemsidation of 2-indolone compounds and their derivatives, characterized in that: include, The 2-indolone compounds and their derivatives shown in Formula I and the diselenide compounds shown in Formula II were dissolved in a solvent at room temperature and in an air atmosphere, and then reacted under a constant current in the presence of an electrolyte to obtain the target compound shown in Formula III. R 3 -Se-Se-R 3 (Formula II); Among them, R 1 It is selected from one of methyl, methoxy, pinacol borate, halogen, trifluoromethyl, cyano, nitro, and methyl formate. R 2 Selected from one of hydrogen, methyl, and phenyl; R 3 It is selected from one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-halophenyl, 4-trifluorotolyl, 2-thienyl, 2-naphthyl, methyl, ethyl, and benzyl.

2. The electrochemically promoted gemiselenlation reaction method for 2-indolone compounds and their derivatives as described in claim 1, characterized in that: The molar ratio of the 2-indolone compounds and their derivatives to the diselenide compounds is 1:1.

2.

3. The electrochemically promoted gemiselenlation reaction method for 2-indolone compounds and their derivatives as described in claim 1, characterized in that: The 2-indolone compounds and their derivatives include 2-indolone, 5-methyl-2-indolone, 5-methoxy-2-indolone, 5-boronate pinacol ester-2-indolone, 6-methyl-2-indolone, 6-fluoro-2-indolone, 6-chloro-2-indolone, 6-bromo-2-indolone, 5-fluoro-2-indolone, 5-chloro-2-indolone, 5-nitro-2-indolone, 6-trimethyl-2-indolone, etc. One of the following: fluoromethyl-2-indolone, 6-cyano-2-indolone, methyl 6-carboxylate-2-indolone, N-methyl-2-indolone, N-phenyl-2-indolone, 7-aza-2-indolone, 2-benzofuranone, N-acetyl-3-indolone, and 5-(2-(4-(1,2-benzisothiazol-3-yl)-1-piperazinyl)ethyl)-6-chloro-2-indolone.

4. The electrochemically promoted gemiselenlation reaction method for 2-indolone compounds and their derivatives as described in claim 1, characterized in that: The disubstituted diselenide is one of diphenyl diselenide, bis(4-methylphenyl) diselenide, bis(4-methoxyphenyl) diselenide, bis(4-fluorophenyl) diselenide, bis(4-chlorophenyl) diselenide, bis(4-trifluoromethylphenyl), bis(2,2'-thienyl) diselenide, bis(2,2'-naphthyl) diselenide, dimethyl diselenide, diethyl diselenide, and dibenzyl diselenide.

5. The electrochemically promoted gemiselylation reaction method for 2-indolone compounds and their derivatives as described in claim 1, characterized in that: The solvent is one of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, and tetrahydrofuran.

6. The electrochemically promoted gemiselylation reaction method for 2-indolone compounds and their derivatives as described in claim 1, characterized in that: The electrolyte is one of tetrabutylammonium iodide, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium bromide, tetramethylammonium iodide, and ammonium iodide.

7. The electrochemically promoted gemiselylation reaction method for 2-indolone compounds and their derivatives as described in claim 1, characterized in that: In the electrodes used for the constant current reaction, the cathode is an electrode material containing carbon, platinum, and nickel, and the anode is an electrode material containing carbon and platinum.

8. The electrochemically promoted gemiselylation reaction method for 2-indolone compounds and their derivatives as described in claim 7, characterized in that: The constant current reaction has a constant current of 5–15 mA and a reaction time of 1–2 hours.

9. The gemdiselenated product obtained by the electrochemically promoted gemdiselenation reaction method of any one of claims 1 to 8 for 2-indole ketone compounds and their derivatives.

10. The use of the gem-diselenylated product as described in claim 9 in inhibiting plant growth or in the preparation of drugs for inhibiting plant growth, characterized in that: The plant fungi include one or more of the following: grape bud fungus, stone fruit brown rot fungus, and apple ring rot fungus.

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