A selenium compound containing a nitrogen-containing heteroarene and a synthesis process thereof

Abstract

The application discloses a nitrogen-containing heteroarene selenium compound and a synthesis process thereof, and a structure of the compound is shown in a formula (1). In the formula (1), a substituent group R includes at least one of hydrogen, halogen, methyl, carboxyl and phenyl. The synthesis process of the nitrogen-containing heteroarene selenium compound is that: under electrochemical conditions, saccharin, diphenyl diselenide and an aryl olefin compound are used as raw materials, and the nitrogen-containing heteroarene selenium compound is generated through reaction. Compared with a traditional method, the application provides a synthesis method of the nitrogen-containing heteroarene selenium compound, which is efficient, environment-friendly and easy to enlarge. The synthesis method is that: under electrochemical conditions, the saccharin, the diphenyl diselenide and the aryl olefin compound are subjected to a double functional group reaction of the olefin, and a functional group of the obtained nitrogen-containing heteroarene selenium compound is good in compatibility.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic selenium compound synthesis, and particularly relates to a selenium compound containing nitrogen heteroarenes and a synthesis process thereof. BACKGROUND

[0002] The information disclosed in the background of the present application is only intended to increase the understanding of the overall background of the present application and should not necessarily be regarded as acknowledging or implicitly suggesting that this information constitutes prior art known to those of ordinary skill in the art.

[0003] Organic compounds containing selenium elements have wide application prospects in the field of pharmacy due to their unique structure and properties, and have good effects in drug oxidation resistance, anticancer and the like. Organic selenium compounds also have great development potential in the fields of biology and materials science. In the existing literature reports on the formation of selenium-containing compounds, the methods used mainly include three types: (1) synthesis of organic selenium compounds under Lewis acid or base catalysis conditions; (2) synthesis of organic selenium compounds under photocatalysis conditions; and (3) synthesis of organic selenium compounds under electrochemical conditions. Among them, the traditional organic reaction method of Lewis acid or base catalysis has high yield, but also has obvious shortcomings, because the acid, base or metal ion used in this reaction is relatively cumbersome to handle, and large-scale application will cause certain harm to the environment, and the above reasons obviously reduce the operability of the reaction. SUMMARY

[0004] In view of the above problems, the present application provides a selenium compound containing nitrogen heteroarenes and a synthesis process thereof, which has technical advantages of high efficiency, environmental protection and easy scaling up compared with the traditional process. To achieve the above purpose, the technical solution of the present application is as follows:

[0005] In the first aspect of the present application, a selenium compound containing nitrogen heteroarenes is disclosed, and the structural formula is shown as formula (1):

[0006]

[0007] In the above formula (1), the substituent group R includes at least one of hydrogen, halogen, methyl, carboxyl and phenyl.

[0008] Further, the halogen includes at least one of F, Cl and Br.

[0009] Further, the number of substitutions of the substituent group R on the benzene ring is 1-5.

[0010] In a second aspect, the synthesis process of the nitrogen-containing heteroarene selenium compound is disclosed, which comprises the following steps: dissolving saccharin, diphenyl diselenide and aryl olefin compound in a solvent, adding a reaction electrolyte, and then performing a reaction under an electrochemical condition.

[0011]

[0012] Further, the substituent R in the aryl olefin compound is the same as the substituent R in the formula (1).

[0013] Further, in the synthesis process, the saccharin, diphenyl diselenide and aryl olefin compound are first dissolved in a solvent, then a reaction electrolyte is added, and then a reaction is performed under an electrochemical condition, after which the target product is separated and purified to obtain the product.

[0014] Further, the solvent comprises at least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile and the like, and is preferably acetonitrile.

[0015] Further, the reaction electrolyte comprises at least one of tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium iodide, tetramethylammonium chloride, tetrabutylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrosulfide and the like, and is preferably tetraethylammonium bromide.

[0016] Further, the molar ratio of the saccharin, diphenyl diselenide, reaction electrolyte and aryl olefin compound is 4:3:2-4:3-6.

[0017] Further, the electrochemistry comprises arranging a cathode and an anode in the reaction electrolyte and applying a current between the cathode and the anode.

[0018] Further, the current is 8-10 mA, and the reaction time is 1.5-3 hours. Under the electrochemical condition, the aryl olefin compound undergoes olefin difunctionalization reaction, thereby synthesizing the target product, i.e., the nitrogen-containing heteroarene selenium compound.

[0019] Further, the reaction temperature is 10-50 DEG C, and preferably, the reaction is performed at room temperature of 20-30 DEG C, so that the reaction is more gentle.

[0020] Further, the anode material comprises any one of graphite, nickel, platinum, iron and the like, and is preferably graphite. When graphite is used as the anode, the reaction effect is the best, and the product yield is higher.

[0021] Further, the cathode material comprises any one of graphite, nickel, platinum, iron and the like, and is preferably nickel material. When nickel is used as the cathode, the reaction effect is the best, and the product yield is higher.

[0022] Compared with the prior art, the present application has at least the following beneficial effects:

[0023] 1. The present application provides a synthesis method of selenium-containing nitrogen heteroarene compounds, which is efficient, environmentally friendly and easy to scale up. The method is based on the double functionalization of olefins under electrochemical conditions using saccharin, diphenyl diselenide and aryl olefins. The resulting selenium-containing nitrogen heteroarene compounds have good functional group compatibility. This is because in the process of the present application, both electron-withdrawing and electron-donating aryl olefins can produce products with moderate or higher yields. For example, electron-donating groups such as methyl, methoxy, tert-butyl, tert-butoxy and acetoxy can produce products with yields of 65-92%; aryl olefins containing halogen atom substituents can produce products with yields of 74-87%; some strong electron-withdrawing groups such as trifluoromethyl and carboxyl can also produce products with moderate yields; 2-vinyl naphthalene and 4-phenyl styrene, which are aryl olefins containing fused ring aromatic hydrocarbons, can produce products with yields of 94% and 93%, respectively; some aryl olefin compounds such as α-methyl styrene, β-methyl styrene and indene containing steric hindrance can produce products with yields of 70%, 87% and 78%, respectively; 2-vinyl thiophene containing heterocycle can produce products with a yield of 84%; even vinyl ferrocene can react in the reaction and produce products with moderate yields. This proves that the process of the present application has high universality and good functional group compatibility, and is suitable for electron-withdrawing and electron-donating aryl olefins. In addition, the process of the present application has the advantages of short reaction time, fast and efficient production of target products, no need for additional metal catalysts and oxidants, and safer technology.

[0024] 2. The reaction of the present application utilizes clean energy, i.e. electricity, and is carried out at normal temperature and pressure without the need for additional oxidants or inert gas protection. The post-reaction treatment operation is simple, no additional oxidants are needed, it is environmentally friendly, the required device is simple, the electrode material can be reused, the reaction is safer and more reliable, the reaction conditions are mild, the operation is simple, the product can be scaled up, the yield is high, and the raw materials are simple and easy to obtain. BRIEF DESCRIPTION OF DRAWINGS

[0025] The accompanying drawings, which form a part of the present application, are used to provide further understanding of the present application, and the schematic embodiments of the present application and their descriptions are used to explain the present application, and do not constitute an improper limitation of the present application. Hereinafter, the embodiments of the present application will be described in detail with reference to the accompanying drawings.

[0026] Figure 1 is the nuclear magnetic resonance hydrogen spectrum of the target product 1a synthesized in the following first embodiment.

[0027] Figure 2is the nuclear magnetic resonance hydrogen spectrum of the target product 1a synthesized in the following first embodiment.

[0028] Figure 3 is the nuclear magnetic resonance hydrogen spectrum of the target product 1b synthesized in the following eighth embodiment.

[0029] Figure 4 is the nuclear magnetic resonance carbon spectrum of the target product 1b synthesized in the following eighth embodiment.

[0030] Figure 5 is the nuclear magnetic resonance hydrogen spectrum of the target product 1c synthesized in the following ninth embodiment.

[0031] Figure 6 is the nuclear magnetic resonance carbon spectrum of the target product 1c synthesized in the following ninth embodiment.

[0032] Figure 7 is the nuclear magnetic resonance hydrogen spectrum of the target product 1d synthesized in the following tenth embodiment.

[0033] Figure 8 is the nuclear magnetic resonance carbon spectrum of the target product 1d synthesized in the following tenth embodiment.

[0034] Figure 9 is the nuclear magnetic resonance hydrogen spectrum of the target product 1e synthesized in the following eleventh embodiment.

[0035] Figure 10 is the nuclear magnetic resonance carbon spectrum of the target product 1e synthesized in the following eleventh embodiment.

[0036] Figure 11 is the nuclear magnetic resonance hydrogen spectrum of the target product 1f synthesized in the following twelfth embodiment.

[0037] Figure 12 is the nuclear magnetic resonance carbon spectrum of the target product 1f synthesized in the following twelfth embodiment.

[0038] Figure 13 is the nuclear magnetic resonance hydrogen spectrum of the target product 1g synthesized in the following thirteenth embodiment.

[0039] Figure 14 is the nuclear magnetic resonance carbon spectrum of the target product 1g synthesized in the following thirteenth embodiment.

[0040] Figure 15 is the nuclear magnetic resonance hydrogen spectrum of the target product 1h synthesized in the following fourteenth embodiment.

[0041] Figure 16 is the nuclear magnetic resonance carbon spectrum of the target product 1h synthesized in the following fourteenth embodiment.

[0042] Figure 17is the nuclear magnetic resonance hydrogen spectrum of the target product 1i synthesized in the following fifteenth embodiment.

[0043] Figure 18 is the nuclear magnetic resonance carbon spectrum of the target product 1i synthesized in the following fifteenth embodiment.

[0044] Figure 19 is the nuclear magnetic resonance hydrogen spectrum of the target product 1j synthesized in the following sixteenth embodiment.

[0045] Figure 20 is the nuclear magnetic resonance carbon spectrum of the target product 1j synthesized in the following sixteenth embodiment.

[0046] Figure 21 is the nuclear magnetic resonance hydrogen spectrum of the target product 1k synthesized in the following seventeenth embodiment.

[0047] Figure 22 is the nuclear magnetic resonance carbon spectrum of the target product 1k synthesized in the following seventeenth embodiment.

[0048] Figure 23 is the nuclear magnetic resonance hydrogen spectrum of the target product 1l synthesized in the following eighteenth embodiment.

[0049] Figure 24 is the nuclear magnetic resonance carbon spectrum of the target product 1l synthesized in the following eighteenth embodiment.

[0050] Figure 25 is the nuclear magnetic resonance hydrogen spectrum of the target product 1m synthesized in the following nineteenth embodiment.

[0051] Figure 26 is the nuclear magnetic resonance carbon spectrum of the target product 1m synthesized in the following nineteenth embodiment.

[0052] Figure 27 is the nuclear magnetic resonance hydrogen spectrum of the target product 1n synthesized in the following twentieth embodiment.

[0053] Figure 28 is the nuclear magnetic resonance carbon spectrum of the target product 1n synthesized in the following twentieth embodiment.

[0054] Figure 29 is the nuclear magnetic resonance hydrogen spectrum of the target product 1o synthesized in the following twenty-first embodiment.

[0055] Figure 30 is the nuclear magnetic resonance carbon spectrum of the target product 1o synthesized in the following twenty-first embodiment.

[0056] Figure 31 is the nuclear magnetic resonance hydrogen spectrum of the target product 1p synthesized in the following twenty-second embodiment.

[0057] Figure 32is the nuclear magnetic resonance hydrogen spectrum of the target product 1p synthesized by the following twenty-second embodiment.

[0058] Figure 33 is the nuclear magnetic resonance hydrogen spectrum of the target product 1q synthesized by the following twenty-third embodiment.

[0059] Figure 34 is the nuclear magnetic resonance carbon spectrum of the target product 1q synthesized by the following twenty-third embodiment.

[0060] Figure 35 is the nuclear magnetic resonance hydrogen spectrum of the target product 1r synthesized by the following twenty-fourth embodiment.

[0061] Figure 36 is the nuclear magnetic resonance carbon spectrum of the target product 1r synthesized by the following twenty-fourth embodiment.

[0062] Figure 37 is the nuclear magnetic resonance hydrogen spectrum of the target product 1s synthesized by the following twenty-fifth embodiment.

[0063] Figure 38 is the nuclear magnetic resonance carbon spectrum of the target product 1s synthesized by the following twenty-fifth embodiment.

[0064] Figure 39 is the nuclear magnetic resonance hydrogen spectrum of the target product 1t synthesized by the following twenty-sixth embodiment.

[0065] Figure 40 is the nuclear magnetic resonance carbon spectrum of the target product 1t synthesized by the following twenty-sixth embodiment.

[0066] Figure 41 is the nuclear magnetic resonance hydrogen spectrum of the target product 1u synthesized by the following twenty-seventh embodiment.

[0067] Figure 42 is the nuclear magnetic resonance carbon spectrum of the target product 1u synthesized by the following twenty-seventh embodiment.

[0068] Figure 43 is the nuclear magnetic resonance hydrogen spectrum of the target product 1v synthesized by the following twenty-eighth embodiment.

[0069] Figure 44 is the nuclear magnetic resonance carbon spectrum of the target product 1v synthesized by the following twenty-eighth embodiment. DETAILED DESCRIPTION

[0070] In the following description, specific details of the application are further set forth for the purpose of fully understanding the application. The description used in this specification uses only the preferred embodiments of the application, and thus should not be used to limit the scope of the application.

[0071] Unless otherwise defined, all technical and scientific terms used in the present disclosure, including to the maximum extent possible, have the meanings that can be commonly understood by one of ordinary skill in the art in the field of the present disclosure. Unless otherwise specified, all drugs or reagents used in the present disclosure are used according to the product instructions or by using conventional methods in the field. The technical solutions of the present disclosure are further described in accordance with the drawings and specific embodiments of the present disclosure.

[0072] First embodiment

[0073] A synthetic process of a selenium-containing compound containing a nitrogen-containing heteroarene, referring to Reaction Scheme 1, comprising:

[0074] (1) In a 10 mL reaction tube, saccharin 3 (37 mg, 0.2 mmol), diphenyl diselenide 4 (47 mg, 0.15 mmol), electrolyte tetraethylammonium bromide (40 mg, 0.2 mmol), styrene 2a (35 μL, 0.3 mmol) and 4 mL solvent acetonitrile were sequentially added.

[0075] (2) In the reaction tube of step (1), an anode electrode and a cathode electrode with length×width×height of 2 mm×8 mm×50 mm were inserted, wherein the material of the anode electrode was graphite and the material of the cathode electrode was metal nickel, the two electrodes were parallel to each other, and the distance between the two electrodes was 10 mm. A constant current of 10 mA was applied between the anode electrode and the cathode electrode, and the reaction was stirred at room temperature 25℃ and in air for 2 h.

[0076]

[0077] (3) Post-treatment: After the reaction was completed, the volatile components in the reaction product were removed under reduced pressure, and then separated by silica gel column chromatography (eluent: petroleum ether (60-90℃) / ethyl acetate, v / v=6:1) to obtain the white solid target product 1a (58 mg, yield 92%).

[0078] The target product 1a was subjected to nuclear magnetic resonance test, and the results are shown in Figure 1 and Figure 2 The structural characterization data are as follows:

[0079] 2-(1-phenyl-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4a): Known compound. (Eluent: petroleum ether (60-90℃) / EtOAc=6:1, v / v). 81.8 mg, 92% yield. White solid. m.p.: 95.8-97.3℃. 1H NMR (CDCI3, 400 MHz) δ 7.99-7.97 (m, 1H), 7.88-7.76 (m, 3H), 7.60-7.56 (m, 4H), 7.38-7.33 (m, 3H), 7.27-7.26 (m, 3H), 5.41 (t, J = 8.1 Hz, 1H), 4.11 (dd, J = 12.9, 7.7 Hz, 1H), 3.84 (dd, J = 12.9, 7.7 Hz, 1H); 13 C NMR (CDCI3, 100 MHz) δ 158.8, 137.4, 136.7, 134.8, 134.4, 133.8, 129.3, 129.1, 128.9, 128.7, 128.6, 127.7, 127.2, 125.2, 120.9, 57.9, 29.1. 3, 100MHz) δ 158.8, 137.4, 136.7, 134.8, 134.4, 133.8, 129.3, 129.1, 128.9, 128.7, 128.6, 127.7, 127.2, 125.2, 120.9, 57.9, 29.1.

[0080] The above test results show that the structural formula of the target product la is as shown in the reaction scheme 1.

[0081] Second embodiment

[0082] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, the reaction steps and operations are the same as those of the above first embodiment, the difference is that the reaction is carried out without electricity. After stirring for 2 h at room temperature 25 °C and in air atmosphere, the results show that the target product la is not obtained, indicating that the selenium-containing nitrogen-containing heteroarene compound cannot be synthesized without electrochemistry: target product la.

[0083] Third embodiment

[0084] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, the reaction steps and operations are the same as those of the above first embodiment, the difference is that the solvent is methanol. The difference is that the reaction is carried out without electricity. After stirring for 2 h at room temperature 25 °C and in air atmosphere, the results show that the target product la is not obtained, indicating that the use of protic solvent is not conducive to the reaction.

[0085] Fourth embodiment

[0086] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, the reaction steps and operations are the same as those of the above first embodiment, the difference is that the reaction does not add electrolyte tetraethylammonium bromide. The difference is that the reaction is carried out without electricity. After stirring for 2 h at room temperature 25 °C and in air atmosphere, the results show that the target product la is not obtained, indicating that the reaction is difficult to proceed without electrolyte.

[0087] Fifth embodiment

[0088] A synthesis process of a nitrogen-containing heteroarene selenium compound, the reaction steps and operations are the same as the above first embodiment, the difference is that: saccharin: diphenyl diselenide: tetraethylammonium bromide: styrene = 4:3:2:3 are added into the reaction tube in turn, the current is 8 mA, the temperature is 50 ℃, and stirring is carried out in air atmosphere for 1.5 h, then processing, the results show that: the target product is generated, the yield is lower than that of example one.

[0089] Sixth embodiment

[0090] A synthesis process of a nitrogen-containing heteroarene selenium compound, the reaction steps and operations are the same as the above first embodiment, the difference is that: the reaction electrolyte is tetraethylammonium chloride, stirring is carried out at 30 ℃ and in air atmosphere for 3 h, then processing, the results show that: the target product is generated, the yield is lower than that of example one.

[0091] Seventh embodiment

[0092] A synthesis process of a nitrogen-containing heteroarene selenium compound, the reaction steps and operations are the same as the above first embodiment, the difference is that: the reaction electrolyte is tetraethylammonium chloride, stirring is carried out at 10 ℃ and in air atmosphere for 3 h, then processing, the results show that: the target product is generated, the yield is lower than that of example one.

[0093] Eighth embodiment

[0094] A synthesis process of a nitrogen-containing heteroarene selenium compound, referring to reaction route 2, the reaction steps and operations are the same as the above first embodiment, the difference is that: the styrene 2a is replaced by 4-methylstyrene 2b (40 μL, 0.3 mmol). Stirring is carried out at room temperature 25 ℃ and in air atmosphere for 2 h, then processing, the target product 1b (73.5 mg, yield 76%) is obtained as colorless oil after post-processing.

[0095]

[0096] The target product 1b is tested by nuclear magnetic resonance, the results are shown in Figure 3 and Figure 4 , and the structure characterization data are as follows:

[0097] 2-(2-(phenylselanyl)-1-(p-tolyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4b): Known compound. (Eluent: petroleum ether (60-90 ℃) / EtOAc = 6:1, v / v). 73.5 mg, 76% yield. Colorless oil.1 H NMR (CDC13, 400 MHz) δ 7.97-7.95 (m, 1H), 7.85-7.73 (m, 3H), 7.57-7.55 (m, 2H), 7.47 (d, J = 8.1 Hz, 2H), 7.26-7.24 (m, 3H), 7.16 (d, J = 8.1 Hz, 2H), 5.38 (t, J = 8.1 Hz, 1H), 4.06 (dd, J = 12.8, 8.3 Hz, 1H), 3.83 (dd, J = 12.8, 7.9 Hz, 1H), 2.83 (s, 3H); 13 C NMR (CDC13, 100 MHz) δ 158.8, 138.8, 137.5, 134.5, 134.3, 133.8, 133.7, 129.4, 129.3, 129.2, 128.6, 127.7, 127.2, 125.2, 120.8, 57.6, 29.1, 21.3. 3, 100MHz) δ 158.8, 138.8, 137.5, 134.5, 134.3, 133.8, 133.7, 129.4, 129.3, 129.2, 128.6, 127.7, 127.2, 125.2, 120.8, 57.6, 29.1, 21.3.

[0098] The above test results show that the structural formula of the target product 1b is as shown in the reaction scheme 2.

[0099] Ninth embodiment

[0100] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, referring to reaction scheme 3, the reaction steps and operations are the same as those of the first embodiment described above, the difference is that the styrene 2a is replaced by 2,5-dimethylstyrene 2c (40 μL, 0.3 mmol). After stirring at room temperature 25°C and in air atmosphere for 2h, the treatment is carried out, and the target product 1c (61.4 mg, yield 65%) in colorless oil is obtained after post-treatment.

[0101]

[0102] The target product 1c is subjected to nuclear magnetic resonance test, and the results are as shown in Figure 5 and Figure 6 The structural characterization data are as follows:

[0103] 2-(1-(2,5-dimethylphenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4c): New compound. (Eluent: petroleum ether (60-90°C) / EtOAc = 6:1, v / v). 61.4 mg, 65% yield. Colorless oil. 1H NMR (CDC13, 400 MHz) δ 8.05-8.02 (m, 1H), 7.83-7.77 (m, 3H), 7.57-7.55 (m, 2H), 7.52 (s, 1H), 7.27-7.23 (m, 3H), 7.04 (s, 2H), 5.71 (t, J = 8.0 Hz, 1H), 4.04 (dd, J = 12.9, 8.2 Hz, 1H), 3.72 (dd, J = 12.9, 7.8 Hz, 1H), 2.31 (s, 3H), 2.22 (s, 3H); 13 C NMR (CDC13, 100 MHz) δ 159.2, 137.8, 135.9, 134.9, 134.3, 134.2, 133.98, 133.9, 130.7, 129.7, 129.4, 129.2, 128.6, 127.8, 127.1, 125.4, 120.7, 54.3, 30.1, 21.4, 19.0. HRMS (ESI-Orbitrap) m / z calcd for C 23 H 21 NO3SSeNa[M+Na] + : 494.02996; found: 492.02997.

[0104] The above test results show that the structural formula of the target product 1c is as shown in the reaction scheme 3.

[0105] Tenth embodiment

[0106] A synthesis process of a nitrogen-containing heteroarene selenium compound, referring to reaction scheme 4, the reaction steps and operations are the same as those of the first embodiment, the difference is that the styrene 2a is replaced by 4-tert-butyl styrene 2d (55 μL, 0.3 mmol). After stirring at room temperature 25°C and in air atmosphere for 2h, the target product 1d (88 mg, yield 88%) is obtained as colorless oil after post-treatment.

[0107]

[0108] The target product 1d is subjected to nuclear magnetic resonance test, and the results are as shown in Figure 7 and Figure 8 The structural characterization data are as follows:

[0109] 2-(1-(4-(tert-butyl)phenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4d): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6:1, v / v). 88 mg, 88% yield. Colorless oil. 1 H NMR (CDCI3, 400 MHz) δ 7.96-7.94 (m, 1H), 7.86-7.72 (m, 3H), 7.58-7.56 (m, 2H), 7.54-7.51 (m, 2H), 7.40-7.36 (m, 2H), 7.27-7.23 (m, 3H), 5.41 (t, J = 7.5 Hz, 1H), 4.14 (dd, J = 13.0, 8.8 Hz, 1H), 3.83 (dd, J = 12.9, 7.4 Hz, 1H), 1.31 (s, 9H); 13 C NMR (CDCI3, 100 MHz) δ 158.8, 151.7, 137.5, 134.8, 134.3, 133.9, 133.8, 129.2, 129.2, 128.3, 127.7, 127.3, 125.6, 125.2, 120.9, 57.8, 34.7, 31.4, 29.3.

[0110] The above test results show that the structural formula of the target product 1d is as shown in the reaction scheme 4.

[0111] Eleventh embodiment

[0112] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, referring to reaction scheme 5, the reaction steps and operations are the same as those of the first embodiment, the difference is that the styrene 2a is replaced by 4-methoxystyrene 2e (40 μL, 0.3 mmol). After stirring at room temperature 25 °C and in air atmosphere for 2 h, the target product 1e (62.1 mg, yield 66%) is obtained as colorless oil after post-treatment.

[0113]

[0114]

[0115] The target product 1e was subjected to nuclear magnetic resonance test, and the results are shown in Figure 9 and Figure 10 The structural characterization data are as follows:

[0116] 2-(1-(4-methoxyphenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4e): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6:1, v / v). 62.1 mg, 66% yield. Colorless oil. 1 H NMR (CDC13, 400 MHz) δ 7.95 (d, J = 7.5 Hz, 1H), 7.84-7.73 (m, 3H), 7.56-7.49 (m, 4H), 7.25-7.23 (m, 3H), 6.86 (d, J = 8.7 Hz, 2H), 5.36 (t, J = 8.1 Hz, 1H), 4.03 (dd, J = 12.8, 8.1 Hz, 1H), 3.82 (dd, J = 12.8, 8.1 Hz, 1H), 3.78 (s, 3H); 13 C NMR (CDC13, 100 MHz) δ 159.9, 158.8, 137.5, 134.8, 134.4, 133.8, 130.1, 129.3, 129.2, 128.6, 127.7, 127.3, 125.2, 120.9, 114.0, 57.5, 55.4, 29.3.

[0117] The above test results show that the structural formula of the target product 1e is as shown in the reaction scheme 5.

[0118] Twelfth embodiment

[0119] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, referring to reaction scheme 6, the reaction steps and operations are the same as those of the first embodiment, the difference is that the styrene 2a is replaced by 4-tert-butoxy styrene 2f (56 μL, 0.3 mmol). After stirring at room temperature 25 °C and in air atmosphere for 2 h, the white solid target product 1f (85.3 mg, yield 83%) is obtained after post-treatment.

[0120]

[0121] The target product 1f is subjected to nuclear magnetic resonance test, and the results are as shown in Figure 11 and Figure 12 The structural characterization data are as follows:

[0122] 2-(1-(4-(tert-butoxy)phenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4f): New compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6:1, v / v). 85.3 mg, 83% yield. White solid. m.p.: 136.6-138.6 °C. 1 H NMR (CDC13, 400 MHz) δ 7.98-7.96 (m, 1H), 7.87-7.76 (m, 3H), 7.56-7.54 (m, 2H), 7.47-7.43 (m, 2H), 7.26-7.23 (m, 3H), 6.95-6.92 (m, 2H), 5.36 (t, J = 8.0 Hz, 1H), 4.08 (dd, J = 12.8, 8.7 Hz, 1H), 3.77 (dd, J = 12.8, 7.5 Hz, 1H), 1.33 (s, 9H); 13 C NMR (CDC13, 100 MHz) δ 158.8, 156.0, 137.5, 134.8, 134.4, 133.9, 131.3, 129.4, 129.3, 129.2, 127.7, 127.3, 125.3, 123.8, 120.9, 78.8, 57.6, 29.4, 29.0. HRMS (ESI-Orbitrap) m / z calcd for C 25 H 25 NO4SSeNa[M+Na] + : 538.05617; found: 538.05615.

[0123] The above test results show that the structural formula of the target product 1f is as shown in the reaction scheme 6.

[0124] Thirteenth embodiment

[0125] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, referring to reaction scheme 7, the reaction steps and operations are the same as those of the first embodiment, the difference is that the styrene 2a is replaced by 5-vinylbenzo[D][1,3]dioxol 2g (38 μL, 0.3 mmol).

[0126] After stirring at room temperature 25 °C and in air atmosphere for 2 h, the white solid target product 1g (84 mg, yield 84%) was obtained after post-treatment.

[0127]

[0128] The target product 1g was subjected to nuclear magnetic resonance test, and the results are shown in Figure 13 and Figure 14 The structural characterization data are as follows:

[0129] 2-(1-(benzo[d][1,3]dioxol-5-yl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide(4g):New compound.(Eluent:petroleum ether(60-90℃) / EtOAc=6:1,v / v).84mg,84%yield.White solid.m.p.127.4-128.6℃: 1 H NMR (CDCI3, 400 MHz) δ 7.98-7.96 (m, 1H), 7.87-7.76 (m, 3H), 7.56-7.53 (m, 2H), 7.27-7.24 (m, 3H), 7.09 (d, J = 1.84 Hz, 1H), 7.03 (dd, J = 8.12, 1.84 Hz, 1H), 6.76 (d, J = 8.08 Hz, 1H), 5.94-5.93 (m, 2H), 5.31 (t, J = 16.2 Hz, 1H), 3.99 (dd, J = 12.84, 8.04 Hz, 1H), 3.79 (dd, J = 12.88, 8.16 Hz, 1H); 13 C NMR (CDCI3, 100 MHz) δ 158.8, 148.0, 147.9, 137.4, 134.9, 134.4, 133.8, 130.4, 129.3, 129.0, 127.7, 127.2, 125.3, 122.7, 120.9, 109.1, 108.2, 101.4, 57.9, 29.3; HRMS (ESI-Orbitrap) m / z calcd for C 22 H 17 NO5SSeNa[M+Na] + :509.98849; found:509.98871.

[0130] The above test results show that the structural formula of the target product 1g is as shown in the reaction scheme 7.

[0131] Fourteenth embodiment

[0132] A synthetic process of a selenium-containing compound with nitrogen-containing heteroarenes, referring to Reaction Scheme 8, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 1-(chloromethyl)-3-styrene 2h (43 μL, 0.3 mmol). After stirring at room temperature 25 °C and air atmosphere for 2 h, the treatment is carried out, and the white solid target product 1h (74 mg, yield 75%) is obtained after post-treatment.

[0133]

[0134] The target product 1h was subjected to nuclear magnetic resonance test, and the results are shown in Figure 15 and Figure 16 The structural characterization data are as follows:

[0135] 2-(1-(3-(chloromethyl)phenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4h): New compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6:1, v / v). 74.1 mg, 75% yield. Colorless oil. 1 H NMR (CDCI3, 400 MHz) δ 7.97-7.95 (m, 1H), 7.87-7.75 (m, 3H), 7.57-7.53 (m, 2H), 7.37-7.35 (m, 2H), 7.27-7.24 (m, 3H), 5.38 (t, J = 8.1 Hz, 1H), 4.56 (s, 2H), 4.06 (dd, J = 12.9, 8.24 Hz, 1H), 3.81 (dd, J = 12.9, 7.9 Hz, 1H); 13 C NMR (CDCI3, 100 MHz) δ 158.73, 137.9, 137.3, 136.9, 134.8, 134.3, 133.8, 129.3, 129.2, 129.1, 129.0, 128.8, 128.8, 127.8, 127.1, 125.2, 120.8, 57.5, 45.7, 28.9; HRMS (ESI-Orbitrap) m / z calcd for C 22 H 18 ClNO3SSeNa[M+Na] + :513.97533; found:513.97504.

[0136] The above test results show that the structural formula of the target product 1h is as shown in the said reaction scheme 8.

[0137] Fifteenth embodiment

[0138] A synthetic process of a selenium-containing nitrogenous heteroarene compound, referring to Reaction Scheme 9, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 3-fluorostyrene 2i (36 μL, 0.3 mmol). After stirring at room temperature 25℃ and air atmosphere for 2h, the treatment is carried out, and the target product 1i (70.6 mg, yield 77%) is obtained by post-treatment as colorless oil.

[0139]

[0140] The target product 1i is tested by nuclear magnetic resonance, and the results are shown in Figure 17 and Figure 18 The structural characterization data are as follows:

[0141] 2-(1-(3-fluorophenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4i): New compound. (Eluent: petroleum ether (60-90℃) / EtOAc = 6:1, v / v). 70.6 mg, 77% yield. White solid. m.p.: 112-113℃. 1 H NMR (CDCI3, 400 MHz) δ 7.97-7.95 (m, 1H), 7.87-7.75 (m, 3H), 7.55-7.52 (m, 2H), 7.45 (s, 4H), 7.26-7.22 (m, 2H), 5.33 (t, J = 8.1 Hz, 1H), 4.02 (dd, J = 12.9, 7.9 Hz, 1H), 3.81 (dd, J = 12.9, 8.3 Hz, 1H); 13 CNMR (CDCI3, 100 MHz) δ 164.0, 161.5, 158.8, 139.2 (d, J = 7.2 Hz), 137.4, 135.0, 134.5, 134.0, 130.2 (d, J = 8.1 Hz), 129.4, 128.8, 127.9, 127.1, 125.4, 124.4 (d, J = 2.9 Hz), 120.9, 115.8 (dd, J = 21.8, 8.3 Hz), 57.3, 28.9. HRMS (ESI-Orbitrap) m / z calcd for C 21 H 17 NO3SSe[M+H] +: 462.00729; found: 462.00766.

[0142] The above test results show that the target product 1i has the structural formula as shown in the reaction scheme 9.

[0143] Sixteenth embodiment

[0144] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, referring to reaction scheme 10, the reaction steps and operations are the same as the above first embodiment, the difference is that the styrene 2a is replaced by 4-chlorostyrene 2j (40 μL, 0.3 mmol). After stirring at room temperature 25℃ and air atmosphere for 2h, treatment is carried out, and the target product 1j (82.7mg, yield 87%) is obtained by post-treatment.

[0145]

[0146] The target product 1j is subjected to nuclear magnetic resonance test, and the results are as shown in Figure 19 and Figure 20 The structural characterization data are as follows:

[0147] 2-(1-(4-chlorophenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (3j): Known compound. (Eluent: petroleum ether (60-90℃) / EtOAc = 6:1, v / v). 82.7mg, 87% yield. Colorless oil. 1 H NMR (CDCI3, 400 MHz) δ 7.97-7.95 (m, 1H), 7.87-7.75 (m, 3H), 7.55-7.49 (m, 4H), 7.32-7.24 (m, 5H), 5.35 (t, J = 8.1 Hz, 1H), 4.03 (dd, J = 12.9, 7.9 Hz, 1H), 3.81 (dd, J = 12.9, 8.2 Hz, 1H); 13 C NMR (CDCI3, 100 MHz) δ 158.8, 137.4, 135.1, 135.0, 134.8, 134.5, 133.9, 130.2, 129.4, 128.8, 128.8, 127.9, 127.1, 125.3, 120.9, 57.2, 28.8.

[0148] The above test results show that the target product 1j has the structural formula as shown in the reaction scheme 10. The above test results show that the target product 1i has the structural formula as shown in the reaction scheme 9.

[0143] Sixteenth embodiment

[0144] A synthesis process of a selenium-containing nitrogen-containing heteroarene compound, referring to reaction scheme 10, the reaction steps and operations are the same as the above first embodiment, the difference is that the styrene 2a is replaced by 4-chlorostyrene 2j (40 μL, 0.3 mmol). After stirring at room temperature 25℃ and air atmosphere for 2h, treatment is carried out, and the target product 1j (82.7mg, yield 87%) is obtained by post-treatment.

[0145]

[0146] The target product 1j is subjected to nuclear magnetic resonance test, and the results are as shown in Figure 19 and Figure 20 The structural characterization data are as follows:

[0147] 2-(1-(4-chlorophenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (3j): Known compound. (Eluent: petroleum ether (60-90℃) / EtOAc = 6:1, v / v). 82.7mg, 87% yield. Colorless oil. 1 H NMR (CDCI3, 400 MHz) δ 7.97-7.95 (m, 1H), 7.87-7.75 (m, 3H), 7.55-7.49 (m, 4H), 7.32-7.24 (m, 5H), 5.35 (t, J = 8.1 Hz, 1H), 4.03 (dd, J = 12.9, 7.9 Hz, 1H), 3.81 (dd, J = 12.9, 8.2 Hz, 1H); 13 C NMR (CDCI3, 100 MHz) δ 158.8, 137.4, 135.1, 135.0, 134.8, 134.5, 133.9, 130.2, 129.4, 128.8, 128.8, 127.9, 127.1, 125.3, 120.9, 57.2, 28.8.

[0148] The above test results show that the target product 1j has the structural formula as shown in the reaction scheme 10.

[0149] Seventeenth embodiment

[0150] A synthetic process of a selenium-containing compound of nitrogen-containing heteroarenes, referring to Reaction Scheme 11, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 2-chlorostyrene 2k (38 μL, 0.3 mmol). After stirring at room temperature 25℃ and air atmosphere for 2h, the treatment is carried out, and the target product 1k (70.3 mg, yield 74%) is obtained by post-treatment as a white solid.

[0151]

[0152] The target product 1k is tested by nuclear magnetic resonance, and the results are shown in Figure 21 and Figure 22 The structural characterization data are as follows:

[0153] 2-(1-(2-chlorophenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4k): Known compound. (Eluent: petroleum ether (60-90℃) / EtOAc = 6:1, v / v). 70.3 mg, 74% yield. White solid. m.p.: 167.6-170.5℃. 1 H NMR (CDC13, 400 MHz) δ 8.06-8.03 (m, 1H), 7.83-7.75 (m, 4H), 7.62-7.60 (m, 2H), 7.40-7.38 (m, 1H), 7.32-7.25 (m, 5H), 6.01 (t, J = 8.1 Hz, 1H), 4.01 (dd, J = 13.0, 8.4 Hz, 1H), 3.75 (dd, J = 13.0, 7.8 Hz, 1H); 13 C NMR (CDC13, 100 MHz) δ 159.1, 137.7, 135.0, 134.4, 134.41, 134.2, 133.9, 130.2, 130.0, 129.4, 129.3, 128.9, 127.9, 127.3, 127.0, 125.4, 120.8, 54.2, 29.2.

[0154] The above test results show that the structural formula of the target product 1k is as shown in the reaction scheme 11.

[0155] Eighteenth embodiment

[0156] A synthetic process of a selenium-containing compound with nitrogen-containing heteroarenes, referring to Reaction Scheme 12, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 4-bromostyrene 2l (40 mg, 0.3 mmol). After stirring at room temperature 25℃ and air atmosphere for 2h, the treatment is carried out, and after treatment, the white solid target product 1l (84.5 mg, yield 81%) is obtained.

[0157]

[0158] The target product 1l is tested by nuclear magnetic resonance, and the results are shown in Figure 23 and Figure 24 The structural characterization data are as follows:

[0159] 2-(1-(4-bromophenyl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4l): Known compound. (Eluent: petroleum ether (60-90℃) / EtOAc=6:1, v / v). 84.5 mg, 81% yield. White solid. m.p.: 99.3-105.5℃. 1 H NMR (CDCI3, 400 MHz) δ 7.98-7.96 (m, 1H), 7.88-7.76 (m, 3H), 7.57-7.54 (m, 2H), 7.35-7.24 (m, 6H), 7.03-6.98 (m, 1H), 5.35 (t, J = 8.1 Hz, 1H), 4.05 (dd, J = 13.0, 8.2 Hz, 1H), 3.79 (dd, J = 13.0, 7.9 Hz, 1H); 13 C NMR (CDCI3, 100 MHz) δ 158.7, 137.3, 135.6, 134.9, 134.4, 133.9, 131.8, 130.5, 129.3, 128.7, 127.9, 127.0, 125.3, 123.0, 120.9, 57.2, 28.7.

[0160] The above test results show that the structural formula of the target product 1l is as shown in the reaction scheme 12.

[0161] Nineteenth embodiment

[0162] A synthetic process of a selenium-containing nitrogenous heteroarene, referring to Reaction Scheme 13, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 4-trifluoromethylstyrene 2m (44 μL, 0.3 mmol). After stirring at room temperature 25 °C and air atmosphere for 2 h, the treatment is carried out, and the target product 1m (54.2 mg, yield 53%) is obtained by post-treatment as a colorless oil.

[0163]

[0164] The target product 1m was subjected to nuclear magnetic resonance test, and the results are shown in Figure 25 and Figure 26 The structural characterization data are as follows:

[0165] 2-(2-(phenylselanyl)-1-(4-(trifluoromethyl)phenyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4m): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6: 1, v / v). 54.2 mg, 53% yield. Colorless oil. 1 H NMR (CDCI3, 400 MHz) δ 7.98 (d, J = 7.4 Hz, 1H), 7.89-7.77 (m, 3H), 7.68 (d, J = 8.2 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.54-7.51 (m, 2H), 7.29-7.22 (m, 3H), 5.40 (t, J = 8.1 Hz, 1H), 4.05 (dd, J = 13.0, 7.8 Hz, 1H), 3.84 (dd, J = 13.0, 8.3 Hz, 1H); 13 C NMR (CDCI3, 100 MHz) δ 158.8, 140.6, 137.4, 135.1, 134.5, 134.0, 130.9 (q, J = 32.4 Hz), 129.4, 129.2, 128.6, 128.0, 127.0, 125.6 (q, J = 3.7 Hz), 125.4, 124.0 (q, J = 270.7 Hz), 121.0, 57.4, 28.6.

[0166] The above test results show that the structural formula of the target product 1m is as shown in the said reaction scheme 13.

[0167] Twentieth embodiment

[0168] A synthetic process of a selenium-containing compound of nitrogen-containing heteroarenes, referring to Reaction Scheme 14, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 4-vinylbenzoic acid 2n (38 μL, 0.3 mmol). After stirring at room temperature 25℃ and air atmosphere for 2h, the treatment is carried out, and the white solid target product 1n (59.4mg, yield 61%) is obtained after post-treatment.

[0169]

[0170] The target product 1n was tested by nuclear magnetic resonance, and the results are shown in Figure 27 and Figure 28 The structural characterization data are as follows:

[0171] 4-(1-(1,1-dioxido-3-oxobenzo[d]isothiazol-2(3H)-yl)-2-(phenylselanyl)ethyl)benzoic acid(4n):Known compound.(Eluent:dichloromethane / methyl alcohol=20:1,v / v).59.4mg,61%yield.White solid.m.p.:200.3-201.0℃. 1 H NMR(DMSO-d6,400MHz)δ13.00(s,1H),8.28(d,J=7.56Hz,1H),8.08-7.94(m,5H),7.67(d,J=8.4Hz,2H),7.53-7.51(m,2H),7.29-7.25(m,3H),7.59(d,J=8.9Hz,1H),5.47(t,J=8.04Hz,1H),4.07(dd,J=12.8,8.96Hz,1H),3.93(dd,J=12.76,7.2Hz,1H); 13 C NMR(DMSO-d6,100MHz)δ166.9,158.5,141.7,136.4,136.1,135.4,132.3,130.8,129.5,129.3,128.9,128.3,127.2,125.9,125.3,121.5,56.0,27.9.

[0172] The above test results show that the structural formula of the target product 1n is as shown in the reaction scheme 14.

[0173] Twenty first embodiment

[0174] A synthetic process of a selenium-containing compound with nitrogen-containing heteroarenes, referring to Reaction Scheme 15, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 4-acetoxy styrene 2o (46 μL, 0.3 mmol). After stirring at room temperature 25 °C and air atmosphere for 2 h, the treatment is carried out, and the target product 1o (82 mg, yield 82%) is obtained by post-treatment as a colorless oil.

[0175]

[0176] The target product 1o was tested by nuclear magnetic resonance, and the results are shown in Figure 29 and Figure 30 The structural characterization data are as follows:

[0177] 4-(1-(1,1-dioxido-3-oxobenzo[d]isothiazol-2(3H)-yl)-2-(phenylselanyl)ethyl)phenyl acetate (4o): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 4: 1, v / v). 81.9 mg, 82% yield. Colorless oil. 1 H NMR (CDCI3, 400 MHz) δ 7.95-7.93 (m, 1H), 7.85-7.73 (m, 3H), 7.61-7.54 (m, 4H), 7.27-7.23 (m, 3H), 7.09-7.05 (m, 2H), 5.36 (t, J = 8.0 Hz, 1H), 4.10 (dd, J = 13.0, 8.6 Hz, 1H), 3.78 (dd, J = 13.0, 7.6 Hz, 1H), 2.27 (s, 3H); 13 C NMR (CDCI3, 100 MHz) δ 169.1, 158.6, 150.7, 137.2, 134.7, 134.2, 134.2, 133.8, 129.8, 129.1, 128.7, 127.6, 127.0, 125.01, 121.6, 120.7, 57.15, 28.9, 21.1.

[0178] The above test results show that the structural formula of the target product 1o is as shown in the said reaction scheme 15.

[0179] Twenty second embodiment

[0180] A synthetic process of a selenium-containing compound of nitrogen-containing heteroarene, referring to Reaction Scheme 16, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 4-phenylstyrene 2p (54 mg, 0.3 mmol). After stirring at room temperature 25℃ and air atmosphere for 2h, treatment is carried out, and after treatment, the white solid target product 1p (96.1 mg, yield 93%) is obtained.

[0181]

[0182] The target product 1p is subjected to nuclear magnetic resonance test, and the results are shown in Figure 31 and Figure 32 The structural characterization data are as follows:

[0183] 2-(1-([1,1'-biphenyl]-4-yl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4p): Known compound. (Eluent: petroleum ether (60-90℃) / EtOAc = 6:1, v / v). 96.1 mg, 93% yield. White solid. m.p.: 126.2-128.1℃. 1 HNMR (DMSO, 400 MHz) δ 7.99-7.97 (m, 1H), 7.88-7.75 (m, 3H), 7.67-7.65 (m, 2H), 7.60-7.57 (m, 6H), 7.45-7.41 (m, 2H), 7.37-7.33 (m, 1H), 7.27-7.26 (m, 3H), 5.45 (t, J = 8.1 Hz, 1H), 4.13 (dd, J = 12.9, 8.3 Hz, 1H), 3.89 (dd, J = 12.9, 7.9 Hz, 1H); 13 C NMR (CDCl3, 100 MHz) δ 158.9, 141.7, 140.6, 137.5, 135.7, 134.9, 134.4, 133.9, 129.3, 129.1, 129.1, 128.9, 127.8, 127.6, 127.4, 127.2, 125.3, 120.9, 57.7, 29.1.

[0184] The above test results show that the structural formula of the target product 1p is as shown in the said reaction scheme 16.

[0185] Twenty third embodiment

[0186] A synthetic process of a selenium-containing nitrogenous heteroarene, referring to Reaction Scheme 17, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by 2-vinyl naphthalene 2q (46 mg, 0.3 mmol). After stirring at room temperature 25 °C and air atmosphere for 2 h, the treatment is carried out, and the target product 1q (92.2 mg, yield 94%) is obtained by post-treatment as a colorless oil.

[0187]

[0188] The target product 1q is subjected to nuclear magnetic resonance test, and the results are shown in Figure 33 and Figure 34 The structural characterization data are as follows:

[0189] 2-(1-(naphthalen-2-yl)-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4q): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6: 1, v / v). 92.2 mg, 94% yield. Colorless oil. 1 H NMR (CDCl3, 400 MHz) δ 8.04 (d, 1H), 7.97-7.95 (m, 1H), 7.86-7.70 (m, 7H), 7.60-7.57 (m, 2H), 7.49-7.47 (m, 2H), 7.27-7.25 (m, 3H), 5.60 (t, J = 8.1 Hz, 1H), 4.19 (dd, J = 12.9, 8.2 Hz, 1H), 3.97 (dd, J = 12.9, 8.0 Hz, 1H); 13 C NMR (CDCl3, 100 MHz) δ 158.9, 137.5, 134.8, 134.4, 134.1, 133.9, 133.4, 133.1, 129.3, 129.1, 128.5, 128.5, 128.1, 127.8, 127.7, 127.2, 126.7, 126.4, 126.1, 125.3, 120.9, 58.0, 29.1.

[0190] The above test results show that the structural formula of the target product 1q is as shown in the said reaction scheme 17.

[0191] Twenty fourth embodiment

[0192] A synthetic process of a selenium-containing nitrogenous heteroarene, referring to Reaction Scheme 18, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the styrene 2a is replaced by indene 2r (35 μL, 0.3 mmol). After stirring at room temperature 25 °C and air atmosphere for 2 h, the treatment is carried out, and the target product 1r (71 mg, yield 78%) is obtained by post-treatment as a white solid.

[0193]

[0194] The target product 1r was tested by nuclear magnetic resonance, and the results are shown in Figure 35 and Figure 36 The structural characterization data are as follows:

[0195] 2-(phenylselanyl)-2,3-dihydro-1H-inden-1-yl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4r): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 4: 1, v / v). 71.1 mg, 78% yield. White solid. m.p.: 133.9-134.7 °C. 1 H NMR (CDCI3, 400 MHz) δ 7.98-7.96 (m, 1H), 7.90-7.77 (m, 3H), 7.71-7.68 (m, 2H), 7.33-7.18 (m, 7H), 5.75 (d, J = 7.0 Hz, 1H), 4.67 (dd, J = 14.8, 7.6 Hz, 1H), 3.71 (dd, J = 16.4, 8.0 Hz, 1H), 3.10 (dd, J = 16.4, 7.3 Hz, 1H); 13 C NMR (CDCI3, 100 MHz) δ 158.64, 142.12, 137.70, 137.19, 136.13, 134.93, 134.40, 129.25, 129.12, 128.36, 127.32, 127.19, 125.33, 124.73, 124.55, 120.96, 63.59, 42.51, 38.93.

[0196] The above test results show that the structural formula of the target product 1r is as shown in the reaction scheme 18.

[0197] Twenty fifth embodiment

[0198] A synthetic process of a selenium-containing compound with nitrogen-containing heteroarenes, referring to Reaction Scheme 19, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by a-methylstyrene 2s (39 μL, 0.3 mmol). After stirring at room temperature 25 °C and air atmosphere for 2 h, the treatment is carried out, and the white solid target product 1s (63.7 mg, yield 70%) is obtained after post-treatment.

[0199]

[0200] The target product 1s was tested by nuclear magnetic resonance, and the results are shown in Figure 37 and Figure 38 The structural characterization data are as follows:

[0201] (2-phenyl-1-(phenylselanyl)propan-2-yl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4s): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6: 1, v / v). 63.7 mg, 70% yield. Colorless oil. 1 H NMR (CDCl3, 400MHz) δ 7.89-7.87 (m, 3H), 7.83-7.79 (m, 1H), 7.70-7.69 (m, 2H), 7.54-7.52 (m, 2H), 7.50-7.47 (m, 2H), 7.35-7.24 (m, 3H), 7.11-7.05 (m, 3H), 4.55 (d, J = 12.08 Hz, 1H), 3.89 (d, J = 12.08 Hz, 1H), 2.23 (s, 3H); 13 C NMR (CDCl3, 100MHz) δ 158.9, 143.8, 137.9, 134.7, 134.0, 134.0, 129.6, 128.8, 128.6, 127.6, 127.4, 126.4, 125.5, 125.0, 120.3, 68.0, 37.6, 25.7.

[0202] The above test results show that the structural formula of the target product 1s is as shown in the reaction scheme 19.

[0203] Twenty sixth embodiment

[0204] A synthetic process of a selenium-containing compound with nitrogen-containing heteroarenes, referring to Reaction Scheme 20, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by β-methylstyrene 2t (39 μL, 0.3 mmol). After stirring at room temperature 25 °C and air atmosphere for 2 h, the treatment is carried out, and the white solid target product 1t (83.5 mg, yield 87%) is obtained after post-treatment.

[0205]

[0206] The target product 1t was tested by nuclear magnetic resonance, and the results are shown in Figure 39 and Figure 40 The structural characterization data are as follows:

[0207] 1-phenyl-2-(phenylselanyl)propyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4t): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6: 1, v / v). 83.5 mg, 87% yield. White solid. m.p. 143.8-149.5 °C: 1 H NMR (CDCl3, 400MHz) δ 7.98-7.96 (m, 1H), 7.85-7.74 (m, 3H), 7.65-7.62 (m, 2H), 7.43-7.41 (m, 2H), 7.32-7.28 (m, 4H), 7.25-7.21 (m, 3H), 5.05 (t, J = 11.68, 1H), 4.69-4.61 (m, 1H), 1.56 (d, J = 6.84 Hz, 1H); 13 CNMR (CDCl3, 100MHz) δ 158.7, 137.2, 136.5, 136.5, 136.5, 134.8, 134.4, 129.7, 129.0, 128.9, 128.4, 127.5, 127.1, 125.2, 120.9, 63.4, 37.7, 20.7.

[0208] The above test results show that the structural formula of the target product 1t is as shown in the reaction scheme 20.

[0209] Twenty seventh embodiment

[0210] A synthetic process of a selenium-containing nitrogenous heteroarene, referring to Reaction Scheme 21, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the styrene 2a is replaced by 2-vinylthiophene 2u (31 μL, 0.3 mmol). After stirring at room temperature 25 °C and air atmosphere for 2 h, the treatment is carried out, and the white solid target product 1u (75.2 mg, yield 84%) is obtained after post-treatment.

[0211]

[0212] The target product 1u was tested by nuclear magnetic resonance, and the results are shown in Figure 41 and Figure 42 The structural characterization data are as follows:

[0213] 2-(2-(phenylselanyl)-1-(thiophen-2-yl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4u): Known compound. (Eluent: petroleum ether (60-90 °C) / EtOAc = 6: 1, v / v). 75.2 mg, 84% yield. White solid. m.p.: 89.2-90.4 °C. 1 H NMR (CDCl3, 400MHz) δ 7.99-7.97 (m, 1H), 7.88-7.77 (m, 3H), 7.59-7.56 (m, 2H), 7.28 (dd, J = 5.1, 1.2 Hz, 1H), 7.27-7.23 (m, 4H), 6.97 (dd, J = 5.1, 3.6 Hz, 1H), 5.62 (t, J = 7.9 Hz, 1H), 4.07 (dd, J = 13.0, 8.6 Hz, 1H), 3.81 (dd, J = 13.0, 7.4 Hz, 1H); 13 C NMR (CDCl3, 100MHz) δ 158.6, 139.3, 137.5, 134.9, 134.4, 134.0, 129.3, 128.9, 128.2, 127.9, 127.1, 126.8, 126.5, 125.3, 120.9, 52.8, 30.5.

[0214] The above test results show that the structural formula of the target product 1u is as shown in the reaction scheme 21.

[0215] Twenty eighth embodiment

[0216] A synthetic process of a selenium-containing nitrogenous heteroarene, referring to Reaction Scheme 22, the reaction steps and operations are the same as the above-mentioned first embodiment, the difference is that the said styrene 2a is replaced by vinyl ferrocene 2v (60.9 mg, 0.3 mmol). After stirring at room temperature 25℃ and air atmosphere for 2h, the treatment is carried out, and the yellow solid target product 1v (50.7 mg, yield 45%) is obtained after post-treatment.

[0217]

[0218] The target product 1v is subjected to nuclear magnetic resonance test, and the results are shown in Figure 43 and Figure 44 The structural characterization data are as follows:

[0219] 2-(1-ferrocenyl-2-(phenylselanyl)ethyl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide (4v): New compound. (Eluent: petroleum ether (60-90℃) / EtOAc = 6:1, v / v). 50.7 mg, 45% yield. Yellow solid. m.p.: 152.0-152.2. 1 H NMR (CDC13, 400 MHz) δ 7.95-7.93 (s, 1H), 7.85-7.74 (m, 5H), 7.31-7.29 (m, 3H), 5.34 (dd, J = 11.9, 8.8 Hz, 1H), 4.4 (d, J = 1.0 Hz, 1H), 4.4 (d, J = 1.1 Hz, 1H), 4.19-4.13 (m, 3H), 4.0 (s, 5H), 3.8 (dd, J = 13.3, 10.1 Hz, 1H); 13 C NMR (CDC13, 100 MHz) δ 158.7, 137.7, 135.2, 134.7, 134.2, 129.4, 129.3, 128.2, 127.3, 125.2, 120.8, 84.8, 69.1, 69.0, 68.7, 68.2, 67.7, 54.6, 29.8. HRMS (ESI-Orbitrap) m / z calcd for C 25 H 21 FeNO3SSe[M+H] + : 551.98295; found: 551.98295.

[0220] The above test results show that the structural formula of the target product 1v is as shown in the said reaction scheme 22. The above test results show that the structural formula of the target product 1v is as shown in the said reaction scheme 22.

[0221] The above merely illustrates several embodiments of the present application, and therefore should not be construed as limiting the scope of the patent protection of the present application. It should be noted that other persons skilled in the art can make modifications, substitutions, improvements, etc. without departing from the concept and scope of the present application, and these all belong to the protection scope of the present application. Therefore, the patent protection scope of the present application should be subject to the description according to the claims.

Claims

1. A process for the synthesis of a nitrogen-containing heteroarene selenide compound, characterized in that, The nitrogen-containing heteroarene selenium compound has a structure as shown in formula (1): Formula (1); In the formula (1), the substituent R is selected from halogen, methyl, carboxyl, phenyl, the halogen is selected from at least one of F, Cl and Br, and the number of the substituents on the benzene ring is 1-5; The synthesis process is as follows: first, saccharin, diphenyl diselenide and aryl olefin compound are dissolved in a solvent, then a reaction electrolyte is added, then the reaction is carried out under electrochemical conditions, and after completion, the target product is separated and purified to obtain the product. The aryl olefin compound is shown in formula (2): Formula (2); The substituent R in the formula (2) is the same as the substituent R in the formula (1); The molar ratio of saccharin, diphenyl diselenide, reaction electrolyte, aryl olefin compound is 4:3:2-4:3-6; The reaction electrolyte is tetraethylammonium bromide; The solvent is acetonitrile; The reaction temperature is 20-30℃; The electrochemistry includes: setting a cathode and an anode in the reaction electrolyte, and applying a current between the cathode and the anode; the current is 8-10 mA, and the reaction time is 1.5-3 hours.

2. The process for synthesis of nitrogen-containing heteroarene selenolides according to claim 1, characterized in that, The anode material is selected from any one of graphite, nickel, platinum and iron, and the cathode material is selected from any one of graphite, nickel, platinum and iron.

3. The process for synthesis of nitrogen-containing heteroarene selenolides according to claim 2, characterized in that, The anode material is graphite, and the cathode material is nickel.

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