Synthetic method for constructing beta-amino-organic selenium compound through copper catalysis

Abstract

The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method for constructing a beta-amino-organic selenium compound through copper catalysis. The structural formula of the compound is shown as a general formula X, and the compound with the general formula X is prepared from aryl olefin, aryl selenide, a copper catalyst, an oxidizing agent and a solvent through a one-pot method. Research finds that under the action of an oxidizing agent, aryl selenide is oxidized into selenium positive ions by the oxidizing agent, then aryl olefin is attacked to form a carbocation intermediate, then nitrile nucleophilic attacks carbocation under the catalysis of copper, and then the target beta-amino-organic selenium compound is formed. The synthesis method is low in cost, green, efficient and wide in substrate application range.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic synthesis, and particularly relates to a synthesis method for copper-catalyzed construction of a beta-amino-organoselenium compound. BACKGROUND

[0002] The beta-amino-organoselenium compound is a unique structure of some bioactive molecules and a synthetic intermediate with practical value. It has a wide range of applications in pharmacology, including compounds A with anti-cancer activity and compounds B capable of maintaining the normal body functions of living organisms.

[0003]

[0004] In 1981, the Akio Toshimitsu research group first synthesized the beta-amino-organoselenium compound through electrophilic addition of phenyl selenyl chloride as an electrophilic reagent mediated by trifluoromethanesulfonic acid (J. Org. Chem. 1981, 46, 4727-4733), and in 1989, the Marcello Tiecco research group used diphenyl diselenide as a selenium source and ammonium persulfate as an oxidant to generate phenyl selenide ions in situ to attack olefins to generate beta-amino-organoselenium compounds (Terrahedron 1989, 45, 6819-6832). However, this method uses strong acid as a catalyst, and the substrate has poor universality. In 2015, the Zheng research group and the Zhao research group in 2018 used NaI and KI as catalysts, respectively, and used diaryl diselenide as a selenium source to generate selenium radicals under the action of an oxidant to attack olefins to synthesize beta-amino-organoselenium compounds (Organic Letters 2015, 17, 5444-5447, Current Organic Chemistry, 2018, 22, 613-618). However, the substrate of this method has poor universality and the reaction conditions are harsh. In 2025, the Xu research group used a TBAPF6-mediated electrochemical method to synthesize beta-amino-organoselenium compounds (Green Chem., 2025, 27, 7114-7121). This method has good substrate universality, but a catalytic amount of strong acid is used in the reaction process.

[0005] Therefore, the preparation method of the beta-amino-organoselenium compound still needs to be improved. SUMMARY

[0006] The present application aims at providing a synthesis method for copper-catalyzed construction of beta-amino-organic selenium compounds, which is low in cost, green and efficient, and has a wide range of substrate adaptability.

[0007] To achieve the above-mentioned purposes, the specific technical scheme of the present application is as follows: A beta-amino-organic compound has a structural formula as shown in general formula X.

[0008] General formula X; In the formula, R1 is any one of a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a biphenyl group, a naphthyl group, and a 3,5-dimethylphenyl group. R2 is any one of a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 3-chlorophenyl group, a 2,4,6-trifluorophenyl group, a 4-tert-butylphenyl group, a 3-trifluoromethylphenyl group, a 3,4-dimethylphenyl group, a cyclohexyl group, a 3-(2-ethyl)-indole group, a butyl group, and an ethynyl group. R3 is any one of a methyl group, an ethyl group, a benzyl group, a butyl group, and an isopropyl group.

[0009] A preparation method of a beta-amino-organic selenium compound has a reaction formula as shown in the following formula. .

[0010] The preparation of the compound I, the compound II and the compound III is a prior art, and can also be prepared by referring to the following method. Step one, preparation of the compound I: Mg and iodine are placed in a three-necked flask, THF is injected into the three-necked flask under N2, bromide compound of THF is added dropwise, the mixture is initiated by a hair dryer, and the Grignard reagent compound I is obtained by reacting at 80 DEG C for 4 h.

[0011] Step two, preparation of the compound II: the supernatant of the compound I is transferred to a dry three-necked flask under N2, then elemental selenium is added in batches, the reaction is carried out for 1 h, HCl is added to quench the reaction, ethyl acetate is used for extraction, the organic phases are combined, the organic phase is treated with anhydrous sodium sulfate, and the compound II is obtained after spin-drying.

[0012] Step three, preparation of the compound III: the compound II is dissolved in methanol, and the compound III is obtained by stirring overnight at room temperature under oxygen.

[0013] As a preferred embodiment in the present application, the preparation method of the beta-amino-organic selenium compound comprises the following steps: Under the condition of nitrogen, the compound III, i.e. aryl selenide compound, is mixed with aryl olefin compound, copper salt, oxidant and nitrile in a reaction container, and is stirred and mixed with or without alkali, so that the synthesis reaction is carried out, and finally, the compound IV, i.e. beta-amino-organic selenium compound, is obtained through evaporation and concentration.

[0014] As a preferred embodiment in the present application, in the preparation method of the beta-amino-organic selenium compound, the copper salt is selected from any one of CuCl, CuI, Cu(OAc)2, Cu2O, CuBr and CuOTf2; and more preferably, the copper salt is CuCl.

[0015] As a preferred embodiment in the present application, in the preparation method of the beta-amino-organic selenium compound, the oxidant is selected from any one of K2S2O8, Na2S2O8, H2O2 and TBHP; and more preferably, the oxidant is K2S2O8.

[0016] As a preferred embodiment in the present application, in the preparation method of the beta-amino-organic selenium compound, the molar ratio of aryl olefin compound, aryl selenide compound, copper salt and oxidant is 1:1:0.05:2; and the ratio of the volume of acetonitrile (mL) to the molar amount of potassium persulfate (mmol) is 1:0.6.

[0017] As a preferred embodiment in the present application, in the preparation method of the phenyl phosphoramidate compound, the temperature of the synthesis reaction is 20-100 ℃ (specifically, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, etc.), and more preferably, the temperature is 70 ℃; and the reaction time is 3-7 h (specifically, 3 h, 4 h, 5 h, 6 h, 7 h, etc.), and more preferably, the reaction time is 4 h.

[0018] As a preferred embodiment in the present application, in the preparation method of the beta-amino-organic selenium compound, the synthesis reaction is carried out under the condition of a mixed gas atmosphere composed of any one or more of air, N2 and Ar; and more preferably, the synthesis reaction is carried out under the condition of N2 atmosphere.

[0019] Compared with the prior art, the present application has the following beneficial effects: (1) The preparation method is low in cost, green and efficient, and wide in substrate adaptation range.

[0020] (II) According to the experimental results, it is found that the aryl selenide compound is oxidized into aryl selenide ion under the action of an oxidizing agent, then aryl olefin is formed into aryl olefin positive ion, and then under the catalysis of copper ion, the cyano group attacks the carbon positive ion as a nucleophile, finally the beta-amino-organic selenium compound is generated, the yield is high, reaches more than 60%, and some even reaches more than 90%. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a synthesis route map of the beta-amino-organic selenium compound according to the present application; Fig. 2 is a nuclear magnetic resonance hydrogen spectrum diagram of N-(1-phenyl-2-(phenyl selenyl)ethyl)acetamide in Example 1; Fig. 3 is a nuclear magnetic resonance carbon spectrum diagram of N-(1-phenyl-2-(phenyl selenyl)ethyl)acetamide in Example 1; Fig. 4 is a nuclear magnetic resonance hydrogen spectrum diagram of N-(1-phenyl-2-(4-fluorophenyl selenyl)ethyl)acetamide in Example 2; Fig. 5 is a nuclear magnetic resonance carbon spectrum diagram of N-(1-phenyl-2-(4-fluorophenyl selenyl)ethyl)acetamide in Example 2; Fig. 6 is a nuclear magnetic resonance hydrogen spectrum diagram of N-(1-phenyl-2-(4-chlorophenyl selenyl)ethyl)acetamide in Example 3; Fig. 7 is a nuclear magnetic resonance carbon spectrum diagram of N-(1-phenyl-2-(4-chlorophenyl selenyl)ethyl)acetamide in Example 3; Fig. 8 is a nuclear magnetic resonance hydrogen spectrum diagram of N-(1-phenyl-2-(4-bromophenyl selenyl)ethyl)acetamide in Example 4; Fig. 9 is a nuclear magnetic resonance carbon spectrum diagram of N-(1-phenyl-2-(4-bromophenyl selenyl)ethyl)acetamide in Example 4; Fig. 10 is a nuclear magnetic resonance hydrogen spectrum diagram of N-(1-phenyl-2-((4-(trifluoromethyl)phenyl)selenyl)ethyl)acetamide in Example 5; Fig. 11 is a nuclear magnetic resonance carbon spectrum diagram of N-(1-phenyl-2-((4-(trifluoromethyl)phenyl)selenyl)ethyl)acetamide in Example 5; Fig. 12 is a nuclear magnetic resonance hydrogen spectrum diagram of N-(1-phenyl-2-((3,5-bis(trifluoromethyl)phenyl)selenyl)ethyl)acetamide in Example 6; Fig. 13 is a nuclear magnetic resonance carbon spectrum diagram of N-(1-phenyl-2-((3,5-bis(trifluoromethyl)phenyl)selenyl)ethyl)acetamide in Example 6; Fig. 14 is a nuclear magnetic resonance hydrogen spectrum diagram of N-(1-phenyl-2-((perfluorophenyl)selenyl)ethyl)acetamide in Example 7; Figure 15 is a nuclear magnetic resonance carbon spectrum of N-(l-phenyl-2- ((perfluorophenyl)seleno)ethyl)acetamide in Example 7; Figure 16 is a nuclear magnetic resonance hydrogen spectrum of N-(l-phenyl-(2- naphthalen-2-ylseleno)ethyl)acetamide in Example 8; Figure 17 is a nuclear magnetic resonance carbon spectrum of N-(l-phenyl-(2- naphthalen-2-ylseleno)ethyl)acetamide in Example 8; Figure 18 is a nuclear magnetic resonance hydrogen spectrum of N-(l-(p-tolyl)-2- (phenylseleno)ethyl)acetamide in Example 9; Figure 19 is a nuclear magnetic resonance carbon spectrum of N-(l-(p-tolyl)-2- (phenylseleno)ethyl)acetamide in Example 9; Figure 20 is a nuclear magnetic resonance hydrogen spectrum of N-(l-(4- chlorophenyl)-2-(phenylseleno)ethyl)acetamide in Example 10; Figure 21 is a nuclear magnetic resonance carbon spectrum of N-(l-(4- chlorophenyl)-2-(phenylseleno)ethyl)acetamide in Example 10; Figure 22 is a nuclear magnetic resonance hydrogen spectrum of N-(l-(4- bromophenyl)-2-(phenylseleno)ethyl)acetamide in Example 11; Figure 23 is a nuclear magnetic resonance carbon spectrum of N-(l-(4- bromophenyl)-2-(phenylseleno)ethyl)acetamide in Example 11; Figure 24 is a nuclear magnetic resonance hydrogen spectrum of N-(l-(4- cyanophenyl)-2-(phenylseleno)ethyl)acetamide in Example 12; Figure 25 is a nuclear magnetic resonance carbon spectrum of N-(l-(4- cyanophenyl)-2-(phenylseleno)ethyl)acetamide in Example 12; Figure 26 is a nuclear magnetic resonance hydrogen spectrum of N-(l-(2- chlorophenyl)-2-(phenylseleno)ethyl)acetamide in Example 13; Figure 27 is a nuclear magnetic resonance carbon spectrum of N-(l-(2- chlorophenyl)-2-(phenylseleno)ethyl)acetamide in Example 13; Figure 28 is a nuclear magnetic resonance hydrogen spectrum of N-(2- (phenylseleno)cyclohexyl)acetamide in Example 14; Figure 29 is a nuclear magnetic resonance carbon spectrum of N-(2- (phenylseleno)cyclohexyl)acetamide in Example 14; Figure 30 Figure 30 is a nuclear magnetic resonance hydrogen spectrum of N-(l-(naphthalen- 2-yl)-2-(phenylseleno)ethyl)acetamide in Example 15; Figure 31This is the carbon NMR spectrum of N-(1-(naphth-2-yl)-2-(phenylselenoyl)ethyl)acetamide in Example 15. Detailed Implementation

[0022] All features disclosed in this specification, or all steps in all disclosed methods or processes, may be combined in any way, except for mutually exclusive features and / or steps.

[0023] Any feature disclosed in this specification (including the claims and abstract) may be replaced by other equivalent or similar features, unless specifically stated otherwise. That is, unless specifically stated otherwise, each feature is merely one example of a series of equivalent or similar features.

[0024] The features and performance of the present invention will be further described in detail below with reference to embodiments. Unless otherwise specified, % in the following embodiments refers to volume percentage content; steps not described in detail are conventional techniques.

[0025] The present invention will be further described below with reference to embodiments, but these embodiments are by no means intended to limit the present invention. In all embodiments, 1 H-NMR, 13 C-NMR, measured using a Bruker Avance III 600 MHz NMR spectrometer at the Chengdu Scientific Research Dog testing platform, chemical shifts are expressed as follows: δ (ppm) is used to indicate; Brominated compounds, cuprous chloride, potassium persulfate, and acetonitrile were purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd., while magnesium powder, iodine, selenium, and aryl olefins were purchased from Shanghai Titan Technology Co., Ltd.

[0026] A β-amino-organoselenoside compound, the synthetic route of which is shown below. Figure 1 As shown; The specific synthesis steps are as follows: Aryl olefin compounds, potassium persulfate (200% molar ratio based on aryl olefin compounds), cuprous chloride (5% molar ratio based on aryl olefin compounds), aryl selenide compounds (100% molar ratio based on aryl olefin compounds), and acetonitrile are placed in a reaction vessel and mixed. The mixture is stirred and reacted at 70 °C for 4 h under nitrogen atmosphere. After the reaction is completed, the organic solvent is removed by vacuum distillation. The crude product is separated by column chromatography (Pe:EA = 3:1) to obtain the target product.

[0027] Wherein R1 is any one of phenyl, 2-methylphenyl, 3-methylphenyl, biphenyl, naphthyl, and 3,5-dimethylphenyl; R2 is any one of phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-chlorophenyl, 2,4,6-trifluorophenyl, 4-tert-butylphenyl, 3-trifluoromethylphenyl, 3,4-dimethylphenyl, cyclohexyl, 3-(2-ethyl)-indole, butyl, ethynyl; R3 is any one of methyl, ethyl, benzyl, butyl, isopropyl.

[0028] Example 1: Synthesis of N-(1-phenyl-2-(phenylseleno)ethyl)acetamide

[0029] In the reactor, diphenyl diselenide 0.3 mmol, styrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then under the condition of nitrogen environment, solvent acetonitrile 1 mL was added, and stirred for 4 hours at 70°C, the reaction was stopped and cooled to room temperature, the solvent was removed by reduced pressure distillation, and the crude product was separated by column chromatography to obtain the target product, the yield was 91 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.47 (dd, J = 6.4, 3.1 Hz, 2H), 7.36 (d, J =8.1 Hz, 1H), 7.28 – 7.20 (m, 8H), 5.21 (q, J = 8.0 Hz, 1H), 3.29 (dd, J = 12.5,8.0 Hz, 1H), 3.20 (dd, J = 12.5, 6.1 Hz, 1H), 1.85 (s, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ 169.8, 141.1, 132.6, 129.8, 129.0, 128.4, 127.4, 126.9,126.4, 53.4, 33.6, 22.9. Example 2: Synthesis of N-(1-phenyl-2-(4-fluorophenylseleno)ethyl)acetamide In the reactor was added 4,4'-dichlorodiphenyl diselenide 0.3 mmol, styrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment, stirring at 70 °C for 4 hours, stop the reaction and cool to room temperature, remove the solvent by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 91 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.43 - 7.35 (m, 2H), 7.27 - 7.23 (m, 2H), 7.21 (s, 1H), 7.19 - 7.16 (m, 2H), 6.92 - 6.84 (m, 2H), 6.14 (d, J = 7.6 Hz, 1H), 5.14 (q, J = 7.0 Hz, 1H), 3.27 (dd, J = 12.6, 6.9 Hz, 1H), 3.17 (dd, J = 12.6, 6.5 Hz, 1H), 1.89 (s, 3H). 13 C NMR (151 MHz, Chloroform-d) δ 169.6,163.3, 161.7, 140.6, 135.6, 135.6, 128.8, 127.9, 126.6, 124.1, 124.1, 116.5, 116.3, 53.4, 34.7, 23.3. Example 3: Synthesis of N-(l-phenyl-2-(4-chlorophenylseleno)ethyl)acetamide In the reactor was added 4,4'-dichlorodiphenyl diselenide 0.3 mmol, styrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment, stirring at 70 °C for 4 hours, stop the reaction and cool to room temperature, remove the solvent by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 91 %. 1 H NMR (600 MHz, Chloroform- d ) δ7.33 (s, 1H), 7.31 (s, 1H), 7.25 - 7.19 (m, 3H), 7.17 (d, J = 6.9Hz, 2H), 7.13 (d, J = 8.4 Hz, 2H), 6.28 (d, J = 7.3 Hz, 1H), 5.19 - 5.07 (m, 1H),3.30 (dd, J = 12.6, 6.9 Hz, 1H), 3.17 (dd, J = 12.6, 6.6 Hz, 1H), 1.88 (s, 3H). 13 CNMR (151 MHz, Chloroform- d ) δ 169.8, 140.7, 134.5, 133.7, 129.6, 129.1,128.2, 126.9, 53.6, 34.3, 23.5. Example 4: Synthesis of N-(l-phenyl-2-(4-bromophenylseleno)ethyl)acetamide In the reactor was added 4,4'-dibromodiphenyl diselenide 0.3 mmol, styrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment at 70 °C, continue to stir for 4 hours, stop the reaction and cool to room temperature, remove the solvent under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 89 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.22 (ddd, J = 20.4, 15.2, 7.1 Hz,7H), 7.15 (d, J = 8.1 Hz, 2H), 6.38 (s, 1H), 5.11 (q, J = 7.1 Hz, 1H), 3.27 (dd, J = 12.1, 6.6 Hz, 1H), 3.15 (dq, J = 12.5, 6.6 Hz, 1H), 1.84 (s, 3H).13C NMR (151MHz, Chloroform-d) δ169.7, 140.5, 134.4, 132.2, 128.8, 128.7, 128.0, 126.6, 121.5, 53.4, 34.0, 23.3. Example 5: Synthesis of N-(l-phenyl-2-((4-(trifluoromethyl)phenyl)seleno)ethyl)acetamide In the reactor was added 4,4'-bis(trifluoromethyl)diphenyl diselenide 0.3 mmol, styrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.06 mmol, then added solvent acetonitrile 1 mL under nitrogen environment at 70 °C, continue to stir for 4 hours, stop the reaction and cool to room temperature, remove the solvent under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 60 %. 1 H NMR (600 MHz, Chloroform-d) δ 7.49 (d, J = 8.1 Hz, 2H), 7.41 (d, J = 8.2 Hz, 2H), 7.29 – 7.25 (m, 2H), 7.24 (d, J = 7.0 Hz, 1H), 7.23 – 7.19 (m, 2H), 6.18 (d, J = 7.4 Hz, 1H), 5.21 (q, J = 7.1Hz, 1H), 3.46 (dd, J = 12.6, 6.3 Hz, 1H), 3.27 (dd, J = 12.6, 7.1 Hz, 1H), 1.91(s, 3H). 13C NMR (151 MHz, Chloroform-d) δ 169.7, 140.2, 135.5, 131.8,129.0, 128.2, 126.8, 125.9 (d, J = 3.6 Hz), 125.1, 123.3, 53.5, 33.2,23.2. Example 6: Synthesis of N-(l-phenyl-2-((3,5-bis(trifluoromethyl)phenyl)seleno)ethyl)acetamide In a reactor was added bis[3,5-bis(trifluoromethyl)phenyl]diselenide 0.3 mmol, styrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment, stirring was continued at 70 °C for 4 hours, the reaction was stopped and cooled to room temperature, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, the yield was 76 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.76(s, 2H), 7.64 (s, 1H), 7.25 – 7.20 (m, 5H), 6.53 (d, J = 7.5 Hz, 1H), 5.24 (q, J = 7.3 Hz, 1H), 3.54 (dd, J = 12.5, 6.0 Hz, 1H), 3.33 (dd, J = 12.6, 7.4 Hz, 1H),1.95 (s, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ 169.8, 139.6, 133.2, 132.4 –131.6 (m), 128.9, 128.4, 126.8, 123.9, 122.1, 120.7, 53.7, 34.1, 23.3. Example 7: Synthesis of N-(1-phenyl-2-((perfluorophenyl)seleno)ethyl)acetamide In a reactor was added bis[3,5-bis(trifluoromethyl)phenyl]diselenide 0.3 mmol, styrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment, stirring was continued at 70 °C for 4 hours, the reaction was stopped and cooled to room temperature, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, the yield was 76 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.25 –7.18 (m, 5H), 6.37 (d, J = 7.5 Hz, 1H), 5.20 (q, J= 7.0 Hz, 1H), 3.45 (dd, J = 13.1, 5.4 Hz, 1H), 3.31 (dd, J = 12.6, 7.0 Hz, 1H), 1.98 (s, 3H). 13 C NMR (151 MHz, Chloroform-d) δ 169.7, 147.7, 146.1, 142.2, 140.5, 139.4, 139.4,138.1, 136.5, 128.7, 128.2, 126.6, 101.6, 53.6, 33.7, 23.2. Example 8: Synthesis of N-(l-phenyl-(2-naphthalen-2-ylseleno)ethyl)acetamide In the reactor was added di-2-naphthyl diselenide, 0.3 mmol, styrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment, continuous stirring at 70 °C for 4 hours, stop the reaction and cool to room temperature, remove the solvent under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 74 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.95 (s, 1H), 7.79(d, J = 7.3 Hz, 1H), 7.72 (dd, J = 16.7, 8.6 Hz, 2H), 7.53 (dd, J = 8.5, 1.6 Hz,1H), 7.51 – 7.44 (m, 2H), 7.33 – 7.29 (m, 2H), 7.26 (t, J = 5.9 Hz, 3H), 6.23(s, 1H), 5.31 (q, J = 6.9 Hz, 1H), 3.47 (dd, J = 12.7, 6.8 Hz, 1H), 3.36 (dd, J =12.7, 6.4 Hz, 1H), 1.89 (s, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ169.6, 140.7, 134.0, 132.3, 131.5,130.1, 128.9, 128.7, 128.0, 127.8, 127.4,127.4, 126.7, 126.2, 53.5, 33.9, 23.4. Example 9: Synthesis of N-(1-(p-tolyl)-2-(phenylseleno)ethyl)acetamide

[0030] In the reactor was added diphenyl diselenide 0.3 mmol, p-tolylstyrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment at 70 °C, continuous stirring for 4 hours, stop the reaction and cool to room temperature, remove the solvent by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 80 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.51 – 7.45 (m, 2H), 7.27 – 7.22 (m,3H), 7.16 – 7.11 (m, 4H), 6.03 (d, J = 7.5 Hz, 1H), 5.28 – 5.17 (m, 1H), 3.39(dd, J = 12.6, 6.7 Hz, 1H), 3.28 (dd, J = 12.6, 6.4 Hz, 1H), 2.32 (s, 3H), 1.91(s, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ 169.5, 137.8, 137.7, 132.9, 130.0, 129.5, 129.3, 127.3, 126.5, 53.1, 33.9, 23.4, 21.2. Example 10: Synthesis of N-(1-(4-chlorophenyl)-2-(phenylseleno)ethyl)acetamide In a reactor was added diphenyl diselenide 0.3 mmol, p-chlorostyrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen atmosphere at 70 °C, stirring was continued for 4 hours, the reaction was stopped and cooled to room temperature, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 90 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.46 (dd, J = 6.3, 3.1Hz, 2H), 7.25 (dd, J = 6.5, 4.5 Hz, 5H), 7.16 (d, J = 8.4 Hz, 2H), 6.20 (d, J = 6.9Hz, 1H), 5.19 (q, J = 6.9 Hz, 1H), 3.31 (dd, J = 12.8, 6.9 Hz, 1H), 3.23 (dd, J =12.8, 6.1 Hz, 1H), 1.91 (s, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ 169.7, 139.4, 133.6, 133.1, 129.5, 129.4, 128.9, 128.0, 127.5, 52.9, 33.9, 23.3. Example 11: Synthesis of N-(1-(4-bromophenyl)-2-(phenylseleno)ethyl)acetamide In a reactor was added diphenyl diselenide 0.3 mmol, p-chlorostyrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen atmosphere at 70 °C, stirring was continued for 4 hours, the reaction was stopped and cooled to room temperature, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 90 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.42 – 7.30 (m, 2H),7.27 (d, J = 8.2 Hz, 2H), 7.13 (t,J = 5.3 Hz, 3H), 6.97 (d, J = 8.2 Hz, 2H), 6.10(d, J = 92.8 Hz, 1H), 5.14 – 4.91 (m, 1H), 3.21 – 3.14 (m, 1H), 3.11 (dd, J =11.1, 7.4 Hz, 1H), 1.78 (s, 3H). 13 C NMR (151 MHz, Chloroform-d) δ 169.6, 140.0, 133.2, 131.9, 131.9, 129.4, 128.3, 127.6, 121.7, 53.0, 33.8, 23.3. Example 12: Synthesis of N-(l-(4-cyanophenyl)-2-(phenylseleno)ethyl)acetamide In the reactor was added diphenyl diselenide 0.3 mmol, 4-cyanostyrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment, continuous stirring at 70 °C for 4 hours, stop the reaction and cool to room temperature, remove the solvent under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 77 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.49 (d, J = 8.2 Hz,2H), 7.39 (dd, J = 7.7, 1.6 Hz, 2H), 7.27 (d, J = 8.3 Hz, 2H), 7.22 – 7.16 (m,3H), 6.21 (s, 1H), 5.16 (q, J = 6.8 Hz, 1H), 3.20 (h, J = 7.0 Hz, 2H), 1.88 (s,3H). 13 C NMR (151 MHz, Chloroform- d ) δ169.8, 146.4, 133.4, 132.5, 129.5,128.9, 127.9, 127.3, 118.7, 111.5, 53.2, 33.6, 23.2. Example 13: Synthesis of N-(l-(2-chlorophenyl)-2-(phenylseleno)ethyl)acetamide In the reactor was added diphenyl diselenide 0.3 mmol, 2-chlorostyrene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment, stirring was continued for 4 hours at 70 °C, the reaction was stopped and cooled to room temperature, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 91 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.46 (dd, J = 6.4, 3.0 Hz,2H), 7.27 – 7.22 (m, 2H), 7.22 – 7.19 (m, 3H), 7.14 (pd, J = 7.3, 1.7 Hz, 2H),6.36 (d, J = 7.6 Hz, 1H), 5.53 – 5.42 (m, 1H), 3.29 (qd, J = 12.9, 6.7 Hz, 2H),1.90 (s, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ 169.5, 138.12, 133.3, 132.8,130.2, 129.4, 129.3, 129.0, 128.1, 127.5, 127.1, 51.5, 32.2, 23.3. Example 14: Synthesis of N-(2-(phenylseleno)cyclohexyl)acetamide In the reactor was added diphenyl diselenide 0.3 mmol, cyclohexene 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then solvent acetonitrile 1 mL was added under nitrogen environment, stirring was continued for 4 hours at 70 °C, the reaction was stopped and cooled to room temperature, the solvent was removed by distillation under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 63 %.1 H NMR (600 MHz, Chloroform-d) δ 7.56 (dd, J = 7.3, 2.0 Hz, 2H),7.31 – 7.22 (m, 3H), 5.60 (s, 1H), 3.80 (qd, J = 10.8, 4.1 Hz, 1H), 3.01 (td, J =11.3, 3.8 Hz, 1H), 2.14 (t, J = 15.7 Hz, 2H), 1.89 (s, 3H), 1.67 (t, J = 10.9 Hz,2H), 1.51 (qd, J = 12.4, 3.5 Hz, 1H), 1.33 (q, J = 12.8 Hz, 1H), 1.19 (ddd, J =19.9, 13.9, 10.7 Hz, 2H). 13 C NMR (151 MHz, Chloroform- d ) δ 169.4, 135.5, 129.1, 128.4, 127.9, 53.3, 48.0, 34.1, 33.9, 26.7, 24.7, 23.5. Example 15: Synthesis of N-(1-(naphthalen-2-yl)-2-(phenylseleno)ethyl)acetamide In the reactor was added diphenyl diselenide 0.3 mmol, 2-naphthalenevinyl 0.3 mmol, cuprous chloride 0.05 mmol, potassium persulfate 0.6 mmol, then under nitrogen environment, solvent acetonitrile 1 mL was added at 70 °C, continue to stir for 4 hours, stop the reaction and cool to room temperature, remove the solvent under reduced pressure, the crude product was separated by column chromatography to obtain the target product, yield 76 %. 1 H NMR (600 MHz, Chloroform- d ) δ 7.78 (d, J = 8.7 Hz,3H), 7.70 (s, 1H), 7.53 – 7.43 (m, 4H), 7.35 (dd, J= 8.5, 1.8 Hz, 1H), 7.25 –7.19 (m, 3H), 6.17 (d, J = 7.6 Hz, 1H), 5.42 (q, J = 6.8 Hz, 1H), 3.47 (dd, J =12.7, 6.8 Hz, 1H), 3.38 (dd, J = 12.7, 6.2 Hz, 1H), 1.95 (s, 3H). 13 C NMR (151MHz, Chloroform-d) δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ δ 169.6, 138.1, 133.3, 133.1, 133.0, 129.9, 129.3,128.8, 128.1, 127.8, 127.4, 126.5, 126.2, 125.5, 124.6, 53.5, 33.9,23.4. The above-described examples only express the specific embodiments of the present application, which are described in more detail and in more detail, but cannot be understood as limiting the protection scope of the present application. It should be noted that for those skilled in the art, without departing from the technical concept of the present application, a number of modifications and improvements can be made, which are within the scope of protection of the present application The above-described examples only express the specific embodiments of the present application, which are described in more detail and in more detail, but cannot be understood as limiting the protection scope of the present application. It should be noted that for those skilled in the art, without departing from the technical concept of the present application, a number of modifications and improvements can be made, which are within the scope of protection of the present application.

[0031] This Background section is provided for the purpose of generally presenting the context of the application The work of the present inventors, to the extent it is described in this Background section, and the work of others, to the extent it is described in this Background section, as well as anything described in this section that is not prior art, is not, in and of itself, admitted to be prior art by the present application.

Claims

1. A β-amino-organoselenium compound, characterized in that... Its structural formula is shown in general formula X: General formula X; Wherein R1 is any one of phenyl, 2-methylphenyl, 3-methylphenyl, biphenyl, naphthyl, and 3,5-dimethylphenyl; R2 is any one of phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-chlorophenyl, 2,4,6-trifluorophenyl, 4-tert-butylphenyl, 3-trifluoromethylphenyl, 3,4-dimethylphenyl, cyclohexyl, 3-(2-ethyl)-indole, butyl-n-yl, and ethynyl. R3 is any one of methyl, ethyl, benzyl, butyl, or isopropyl.

2. A method for preparing the β-amino-organoselenium compound as described in claim 1, characterized in that... The reaction formula is as follows: 。 3. The method for preparing the β-amino-organoselenium compound according to claim 2, characterized in that... Includes the following steps: Under nitrogen atmosphere, aryl olefin compounds, aryl selenide compounds, copper salts, oxidants, and acetonitrile are placed in a reaction vessel, stirred, and mixed to carry out a synthesis reaction. Finally, the compound is obtained by vacuum concentration. This compound is β-amino-organoselenium compound.

4. The method for preparing the β-amino-organoselenium compound according to claim 3, characterized in that: The copper catalyst is selected from any one of CuCl, CuI, Cu(OAc)2, Cu2O, CuBr, and CuOTf2.

5. The method for preparing the β-amino-organoselenium compound according to claim 4, characterized in that: The oxidant is selected from any one of K2S2O8, Na2S2O8, H2O2, and TBHP.

6. The method for preparing the β-amino-organoselenium compound according to claim 3, characterized in that: The molar ratio of aryl olefin compounds, aryl selenide compounds, copper salts, and oxidants is 1:1:0.05:2; the ratio of the volume of acetonitrile (mL) to the molar amount of potassium persulfate (mmol) is 1:0.

6.

7. The method for preparing the β-amino-organoselenium compound according to claim 3, characterized in that: The synthesis reaction temperature is 20℃-70℃; the reaction time is 3-7 h.

8. The method for preparing the β-amino-organoselenium compound according to claim 4, characterized in that: The copper catalyst is CuCl.

9. The method for preparing the β-amino-organoselenium compound according to claim 5, characterized in that: The oxidant is K2S2O8.

10. The method for preparing the β-amino-organoselenium compound according to any one of claims 3-9, characterized in that: The synthesis reaction is carried out under a mixed atmosphere consisting of any one or more of air, N2, and Ar.

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