Preparation method of selenium sulfenyl quinoxaline compound

Abstract

The invention discloses a preparation method of a selenium sulfenyl quinoxaline compound. The preparation method comprises the following steps: mixing a compound shown as a formula I, a compound shown as a formula II, a compound shown as a formula III, a copper catalyst, an oxidizing agent and a solvent for reaction, obtaining a compound as shown in a formula IV; the selenium sulfenyl quinoxaline compound is prepared from the compound shown in the formula I, the compound shown in the formula II and the compound shown in the formula III through a one-step method under the action of the copper catalyst and the oxidizing agent, synthesis steps are simple, the raw materials are non-toxic, low in price and easy to obtain, and the synthesis method has the advantages of being good in functional group compatibility, high in atom economy and high in yield.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to a method for preparing selenosulfanyl quinoxaline compounds. Background Art

[0002] Selenosulfanyl quinoxaline and its derivatives are important chemical intermediates, which can be used to synthesize organic semiconductor light-emitting materials, dyes, etc. and have a wide range of biological activities, such as anti-cancer, antibacterial, anti-tumor, anti-viral, anti-inflammatory, etc., and have a wide range of applications in the fields of pesticides and pharmaceuticals. Therefore, the development of efficient synthetic methods for them has attracted much attention.

[0003] Currently reported synthetic methods for selenosulfanyl quinoxaline compounds mainly include the following several: (1) Selective C-H selenylation / sulfenylation reaction; (2) Cross-coupling reaction of aryl halides with diselenides and disulfides. (3) Photocatalytic selective construction of C-Se / C-S bonds. The above synthetic methods have problems such as harsh reaction conditions, cumbersome reaction steps, the need to use equivalent amounts of toxic and harmful reagents, poor selectivity of C-H functionalization, and most of the products are mono-selenated or mono-sulfurized.

[0004] Therefore, it is very necessary to develop a synthetic method for selenosulfanyl quinoxaline compounds with simpler reactions, milder conditions, and higher product yields. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. For this reason, the first aspect of the present invention proposes a method for preparing selenosulfanyl quinoxaline compounds; this preparation method has the advantages of simpler reaction, milder reaction conditions, better reaction selectivity, higher product yield, etc.

[0006] A method for preparing selenosulfanyl quinoxaline compounds according to the first aspect embodiment of the present invention; includes the following steps:

[0007] Mix the compound of formula I, the compound of formula II, the compound of formula III, a copper catalyst, an oxidant and a solvent for reaction; namely, obtain the compound of formula IV;

[0008] The structural formulas of the compound of formula I, the compound of formula II, the compound of formula III and the compound of formula IV are as follows:

[0009]

[0010] R1 is selected from H, C 1～12 alkyl, C 1～12 alkoxy, amino, halogen, phenyl or phenyl substituted by halogen, C 1～6 alkyl;

[0011] R2 is selected from H, C 1～12alkyl group of C 1～12 alkoxy group, amino group, halogen, phenyl group or phenyl group substituted by halogen or alkyl group of C 1～6 alkyl group substituted.

[0012] According to a preferred embodiment of the present invention, the oxidant includes one of iodine, amine iodide, potassium iodide, sodium persulfate, tert-butyl hydroperoxide, and bis(trifluoroacetoxy)iodobenzene.

[0013] According to a preferred embodiment of the present invention, R1 is selected from alkyl group of C 1～6 alkoxy group, amino group, halogen, phenyl group or phenyl group substituted by halogen or alkyl group of C 1～6 alkyl group substituted; 1～3

[0014] According to a preferred embodiment of the present invention, R2 is selected from alkyl group of C 1～6 alkoxy group, amino group, halogen, phenyl group or phenyl group substituted by halogen or alkyl group of C 1～6 alkyl group substituted. 1～3

[0015] According to a preferred embodiment of the present invention, the copper catalyst includes a nano copper catalyst. The copper catalyst has the advantage of being easily separated from the product and can be recycled multiple times.

[0016] According to a preferred embodiment of the present invention, the nano copper catalyst includes nano copper supported on an inorganic material.

[0017] According to a preferred embodiment of the present invention, the nano copper supported on an inorganic material includes at least one of nano copper supported on aluminum oxide, nano copper supported on titanium dioxide, nano copper supported on zinc oxide, nano copper supported on activated carbon, and nano copper supported on manganese oxide.

[0018] According to a preferred embodiment of the present invention, calculated by the molar amount of copper element, the molar ratio of the copper catalyst to the compound of formula I is 0.02 - 0.08:1.

[0019] According to a preferred embodiment of the present invention, the molar ratio of the compound of formula I, the compound of formula II, and the compound of formula III is 1:(1 - 5):(1 - 5).

[0020] According to a preferred embodiment of the present invention, the molar ratio of the oxidant to the compound of formula I is (1 - 5):1.

[0021] According to a preferred embodiment of the present invention, the temperature of the reaction is 25 - 100 °C.

[0022] According to a preferred embodiment of the present invention, the time of the reaction is 1 - 24 h.​​

[0023] According to a preferred embodiment of the present invention, the solvent is at least one of amide solvents, pyridine solvents, alcohol solvents and sulfoxide solvents.

[0024] According to a preferred embodiment of the present invention, the amide solvents include at least one of N-methylformamide, formamide, N-ethylformamide and N,N-dimethylformamide.

[0025] According to a preferred embodiment of the present invention, the pyridine solvents include pyridine.

[0026] According to a preferred embodiment of the present invention, the alcohol solvents include at least one of tert-amyl alcohol, isopropanol, isobutanol and methanol.

[0027] According to a preferred embodiment of the present invention, the sulfoxide solvents include at least one of dimethyl sulfoxide and diphenyl sulfoxide.

[0028] According to a preferred embodiment of the present invention, the preparation method further comprises the following steps: after the reaction is completed, the solvent is removed and then purified.

[0029] According to a preferred embodiment of the present invention, the purification method is column chromatography.

[0030] According to a preferred embodiment of the present invention, the stationary phase used in the column chromatography is silica gel, and the eluent used is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is petroleum ether:ethyl acetate = (1-30):1.

[0031] The preparation method according to the embodiment of the present invention has at least the following beneficial effects:

[0032] The present invention uses a compound of formula I, a compound of formula II and a compound of formula III as raw materials, and under the action of a copper catalyst and an oxidant, a selenosulfanyl quinoxaline compound is prepared by a one-step method. The synthesis steps are not only simple, the raw materials are non-toxic, inexpensive and easily available, and the synthesis method has the advantages of good functional group compatibility, high atom economy and high yield.

[0033] Definitions and general terms

[0034] "C 1～12 alkyl" means an alkyl group having 1 to 12 carbon atoms in total, including C 1～12 straight-chain alkyl, C 1～12 branched-chain alkyl and C 3～12The cycloalkyl group can be, for example, a straight-chain alkyl group with a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, a branched-chain alkyl group with a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or a cycloalkyl group with a total number of carbon atoms of 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. For example, it can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, etc. "C 1～6 alkyl" and C 1～3 alkyl have similar definitions, except for the different total numbers of carbon atoms.

[0035] "C 1～12 alkoxy" represents -O-(unsubstituted alkyl) and -O(unsubstituted cycloalkyl), with a total number of carbon atoms of 1 to 12. Representative examples include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, etc. "C 1～6 alkoxy" has a similar definition, except for the different total numbers of carbon atoms.

[0036] "Halogen" includes fluorine, chlorine, bromine, and iodine.

[0037] Other features and advantages of the present invention will be described in the subsequent specification, and, in part, will become apparent from the specification or will be understood by practicing the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] The above and / or additional aspects and advantages of the present invention will become apparent and be readily understood from the description of the embodiments in conjunction with the following drawings, wherein:

[0039] Figure 1 1H NMR spectrum of the product prepared in Example 1;

[0040] Figure 2 13C NMR spectrum of the product prepared in Example 1;

[0041] Figure 3 1H NMR spectrum of the product prepared in Example 2;

[0042] Figure 4 13C NMR spectrum of the product prepared in Example 2;

[0043] Figure 5 1H NMR spectrum of the product prepared in Example 3;

[0044] Figure 6 13C NMR spectrum of the product prepared in Example 3;

[0045] Figure 71H NMR spectrum of the product prepared in Example 4;

[0046] Figure 8 13C NMR spectrum of the product prepared in Example 4;

[0047] Figure 9 1H NMR spectrum of the product prepared in Example 5;

[0048] Figure 10 13C NMR spectrum of the product prepared in Example 5;

[0049] Figure 11 1H NMR spectrum of the product prepared in Example 6;

[0050] Figure 12 13C NMR spectrum of the product prepared in Example 6;

[0051] Figure 13 1H NMR spectrum of the product prepared in Example 7;

[0052] Figure 14 13C NMR spectrum of the product prepared in Example 7. Detailed Description of the Invention

[0053] The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in combination with the embodiments, but the present invention is not limited to these embodiments.

[0054] The reagents, methods and equipment used in the present invention are all conventional reagents, methods and equipment in the technical field, unless otherwise specified.

[0055] The nano-copper catalyst used in the embodiments of the present invention is prepared by the following method:

[0056] First step, add 0.16 g of anhydrous copper sulfate, 0.36 g of 1,10-phenanthroline, 1 g of carbon powder and 40 mL of absolute ethanol into a 250 mL round-bottom flask, and stir at 70 °C for 12 hours. Filter and wash to obtain a black solid. Second step, calcine the obtained mixture in a tube furnace at 800 °C for 3 h to obtain a carbon material-supported copper nano-catalyst.

[0057] The preparation method of the nano-copper catalyst supported by other materials is the same.

[0058] Example 1

[0059] This example provides a preparation method of a selenosulfur-based quinoxaline compound, and the reaction equation is as follows; including the following steps:

[0060]

[0061] 0.2 mmol of tetrahydroquinoxaline, 0.2 mmol of diphenyldiselenide, 0.3 mmol of diphenyldisulfide, 45 mg of copper metal catalyst supported on activated carbon (activated carbon mass fraction is 3%), 0.15 mmol of iodine, and 2 mL of dimethyl sulfoxide were added to a Schlenk tube (50 mL) equipped with a magnetic stir bar. Under an oxygen atmosphere of 1 atm (using an oxygen balloon), the Schlenk tube was closed and heated at 100 °C for 10 h. After cooling to room temperature, the reaction mixture was filtered. Water (10 mL) and ethyl acetate (30 mL) were added to the resulting layered solution, and then the aqueous layer was extracted with ethyl acetate (2 × 10 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated in vacuo. Further purification by column chromatography was carried out. The stationary phase of the column chromatography used was silica gel, and the eluent was a mixed solvent of petroleum ether and ethyl acetate (petroleum ether:ethyl acetate = 10:1, v / v). The yield of the target product was 65%.

[0062] The 1H NMR spectrum and 13C NMR spectrum of the obtained product are shown respectively as Figure 1 and Figure 2 shown below. The structural characterization data are as follows:

[0063] 1 H NMR (400 MHz, Chloroform-d) δ 8.65 (s, 2H), 7.77 (s, 2H), 7.68 (q, J = 2.4, 1.7 Hz, 2H), 7.66 (d, J = 2.4 Hz, 2H), 7.41 (q, J = 3.1, 2.1 Hz, 4H), 7.39 (d, J = 5.3 Hz, 2H);

[0064] 13 C NMR (101 MHz, Chloroform-d) δ 144.6, 142.2, 139.8, 135.2, 130.9, 130.0, 129.1, 129.0.

[0065] HRMS (ESI): Calcd. For C 20 H 14 N2SSe [M+1] + : 395.0114, found: 395.0118.

[0066] Example 2

[0067] Example 2 provides a method for preparing selenosulfanyl quinoxaline. The reaction equation and preparation method are as follows:

[0068]

[0069] 0.2 mmol of tetrahydroquinoxaline, 0.6 mmol of bis(4-methylphenyl) diselenide, 0.6 mmol of diphenyl disulfide, 60 mg of copper metal catalyst supported on aluminum oxide (the mass fraction of aluminum oxide is 3%), 0.24 mmol of ammonium iodide, and 2 mL of N-methylformamide were added to a schlenk tube (50 mL) equipped with a magnetic stir bar. Under an oxygen atmosphere of 1 atm (using an oxygen balloon), the schlenk tube was closed and heated at 60 °C for 12 h. After cooling to room temperature, the reaction mixture was filtered. Water (10 mL) and ethyl acetate (30 mL) were added to the resulting layered solution, and then the aqueous layer was extracted with ethyl acetate (2 × 10 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated in vacuo. Further purification by column chromatography was carried out. The stationary phase of the column chromatography used was silica gel, and the eluent was a mixed solvent of petroleum ether and ethyl acetate (petroleum ether:ethyl acetate = 15:1, v / v). The yield of the target product was 39%.

[0070] The 1H NMR spectrum and 13C NMR spectrum of the obtained product are shown in Figure 3 and Figure 4 respectively, and the structure characterization data are as follows:

[0071] 1 H NMR (400 MHz, Chloroform-d) δ 8.78 (dd, J = 16.4, 1.6 Hz, 3H), 8.01–7.96 (m, 2H), 7.74–7.66 (m, 3H), 7.50 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 7.1 Hz, 2H), 7.27 (s, 1H), 2.44 (d, J = 3.0 Hz, 3H);

[0072] 13 C NMR (101 MHz, Chloroform-d) δ 145.3, 144.5, 135.3, 134.7, 132.6, 130.7, 129.9, 129.8, 129.6, 128.9, 125.4, 21.3.

[0073] HRMS (ESI): Calcd. For C 21 H 16 N2SSe [M+1] + : 408.0274, found: 408.0271.

[0074] Example 3

[0075] Example 3 provides a preparation method of selenosulfide quinoxaline. The reaction equation and preparation method are as follows:

[0076]

[0077] 0.2 mmol of tetrahydroquinoxaline, 0.6 mmol of bis(4-chlorophenyl) diselenide, 0.4 mmol of diphenyl disulfide, 40 mg of titanium dioxide-supported copper nanoparticles (the mass fraction of titanium dioxide is 3%), 0.2 mmol of sodium iodide, and 2 mL of toluene were added to a Schlenk tube (50 mL) equipped with a magnetic stir bar. Under an oxygen atmosphere of 1 atm (using an oxygen balloon), the Schlenk tube was closed and heated at 60 °C for 16 h. After cooling to room temperature, the reaction mixture was filtered. Water (10 mL) and ethyl acetate (30 mL) were added to the resulting layered solution, and then the aqueous layer was extracted with ethyl acetate (2 × 10 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated in vacuo. Further purification by column chromatography was carried out using silica gel as the stationary phase and a mixed solvent of petroleum ether and ethyl acetate (petroleum ether:ethyl acetate = 8:1, v / v) as the eluent, and the target product was obtained with a yield of 41%.

[0078] The 1H NMR spectrum and 13C NMR spectrum of the obtained product are shown in Figure 5 and Figure 6 respectively, and the structural characterization data are as follows:

[0079] 1 H NMR (400 MHz, Chloroform-d) δ 8.80 (q, J = 1.8 Hz, 3H), 8.00–7.98 (m, 2H), 7.74 (d, J = 1.9 Hz, 1H), 7.69–7.65 (m, 3H), 7.42 (d, J = 1.9 Hz, 3H), 7.40 (s, 1H);

[0080] 13 C NMR (101 MHz, Chloroform-d) δ 145.2, 144.5, 143.4, 141.9, 136.7, 135.4, 132.6, 129.9, 129.8, 129.7, 128.9, 128.3.

[0081] HRMS (ESI): Calcd. For C 20 H 13 ClN2SSe [M+1] + : 428.9726, found: 428.9724.

[0082] Example 4

[0083] Example 4 provides a method for preparing selenosulfanylquinoxaline, and the reaction equation and preparation method are as follows:

[0084]

[0085] 0.2 mmol of tetrahydroquinoxaline, 0.3 mmol of bis(phenyl) diselenide, 0.3 mmol of bis(4-methylphenyl) disulfide, 60 mg of nano copper catalyst supported on activated carbon (the mass fraction of activated carbon is 3%), 0.3 mmol of tert-butyl hydroperoxide, and 2 mL of N,N-dimethylformamide were added to a schlenk tube (50 mL) equipped with a magnetic stir bar. Under an oxygen atmosphere of 1 atm (using an oxygen balloon), the schlenk tube was closed and heated at 80 °C for 8 h. After cooling to room temperature, the reaction mixture was filtered. Water (10 mL) and ethyl acetate (30 mL) were added to the obtained layered solution, and then the aqueous layer was extracted with ethyl acetate (2 × 10 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated in vacuo. Further purification by column chromatography was carried out. The stationary phase of the column chromatography used was silica gel, and the eluent was a mixed solvent of petroleum ether and ethyl acetate (petroleum ether:ethyl acetate = 10:1, v / v). The yield of the target product was 56%.

[0086] The 1H NMR spectrum and 13C NMR spectrum of the obtained product are shown in Figure 7 and Figure 8 respectively, and the structure characterization data are as follows:

[0087] 1 H NMR (400 MHz, Chloroform-d) δ 8.75 (dd, J = 16.4, 1.6 Hz, 3H), 7.98–7.93 (m, 2H), 7.72–7.64 (m, 3H), 7.48 (d, J = 8.0 Hz, 2H), 7.39 (d, J = 7.1 Hz, 2H), 7.24 (s, 1H), 2.41 (d, J = 3.0 Hz, 3H);

[0088] 13 C NMR (101 MHz, Chloroform-d) δ 146.8, 145.1, 138.5, 135.3, 133.2, 130.7, 130.4, 130.0, 129.9, 128.7, 126.5, 121.6, 21.3.

[0089] HRMS (ESI): Calcd. For C 21 H 16 N2SSe [M + 1] + : 409.0277, found: 409.0275.

[0090] Example 5

[0091] Example 5 provides a preparation method of selenosulfide quinoxaline, and the reaction equation and preparation method are as follows:

[0092]

[0093] 0.2 mmol of tetrahydroquinoxaline, 0.5 mmol of bis(phenyl) diselenide, 0.4 mmol of bis(4-chlorophenyl) disulfide, 50 mg of titanium dioxide-supported copper nanoparticles (the mass fraction of titanium dioxide is 3%), 0.24 mmol of sodium persulfate, and 2 mL of dimethyl sulfoxide were added to a Schlenk tube (50 mL) equipped with a magnetic stir bar. Under an oxygen atmosphere of 1 atm (using an oxygen balloon), the Schlenk tube was closed and heated at 100 °C for 16 h. After cooling to room temperature, the reaction mixture was filtered. Water (10 mL) and ethyl acetate (30 mL) were added to the resulting layered solution, and then the aqueous layer was extracted with ethyl acetate (2 × 10 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated in vacuo. Further purification by column chromatography was carried out using silica gel as the stationary phase and a mixed solvent of petroleum ether and ethyl acetate (petroleum ether:ethyl acetate = 30:1, v / v) as the eluent, and the target product was obtained with a yield of 60%.

[0094] The 1H NMR spectrum and 13C NMR spectrum of the obtained product are shown respectively as Figure 9 and Figure 10 shown below, and the structural characterization data are as follows:

[0095] 1 H NMR (400 MHz, Chloroform-d) δ 8.80 (q, J = 1.8 Hz, 3H), 8.00–7.98 (m, 2H), 7.74 (d, J = 1.9 Hz, 1H), 7.69–7.66 (m, 3H), 7.42 (d, J = 1.9 Hz, 3H), 7.40 (s, 1H);

[0096] 13 C NMR (101 MHz, Chloroform-d) δ 145.0, 144.3, 143.2, 141.7, 136.5, 135.2, 132.4, 129.7, 129.6, 129.5, 128.7, 128.1.

[0097] HRMS (ESI): Calcd. For C 20 H 13 ClN2SSe [M+1] + : 428.9726, found: 428.9724.

[0098] Example 6

[0099] Example 6 provides a method for preparing selenosulfanyl quinoxaline, and the reaction equation and preparation method are as follows:

[0100]

[0101] 0.2 mmol of tetrahydroquinoxaline, 0.4 mmol of bis(4-methylphenyl) diselenide, 0.4 mmol of bis(4-chlorophenyl) disulfide, 60 mg of copper catalyst supported on manganese dioxide (mass fraction of manganese dioxide is 3%), 0.1 mmol of sodium persulfate, and 2 mL of methanol were added to a Schlenk tube (50 mL) equipped with a magnetic stir bar. Under an oxygen atmosphere of 1 atm (using an oxygen balloon), the Schlenk tube was closed and heated at 80 °C for 16 h. After cooling to room temperature, the reaction mixture was filtered. Water (10 mL) and ethyl acetate (30 mL) were added to the resulting layered solution, and then the aqueous layer was extracted with ethyl acetate (2 × 10 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated under vacuum. Further purification by column chromatography was carried out. The stationary phase of the column chromatography used was silica gel, and the eluent was a mixed solvent of petroleum ether and ethyl acetate (petroleum ether:ethyl acetate = 20:1, v / v). The yield of the target product was 41%.

[0102] The hydrogen NMR spectrum and carbon NMR spectrum of the obtained product are respectively as Figure 11 and Figure 12 shown, and the structure characterization data are as follows:

[0103] 1 H NMR (400 MHz, Chloroform-d) δ 8.75 (dd, J = 16.4, 1.6 Hz, 3H), 7.98–7.93 (m, 2H), 7.72–7.64 (m, 3H), 7.49 (s, 1H), 7.39 (d, J = 7.1 Hz, 2H), 7.24 (s, 1H), 2.41 (d, J = 3.0 Hz, 3H);

[0104] 13 C NMR (101 MHz, Chloroform-d) δ 146.6, 138.3, 136.4, 135.1, 133.0, 130.5, 130.2, 129.8, 129.8, 128.5, 126.3, 121.4.

[0105] HRMS (ESI): Calcd. For C 21 H 15 ClN2SSe [M+1] + : 442.9881, found: 442.9884.

[0106] Example 7

[0107] Example 7 provides a method for preparing selenosulfanyl quinoxaline. The reaction equation and preparation method are as follows:

[0108]

[0109] 0.2 mmol of tetrahydroquinoxaline, 0.4 mmol of bis(methyl) diselenide, 0.3 mmol of bis(phenyl) disulfide, 60 mg of copper catalyst supported on zinc oxide (the mass fraction of zinc oxide is 3%), 0.15 mmol of iodine, and 2 mL of N,N-dimethylformamide were added to a Schlenk tube (50 mL) equipped with a magnetic stir bar. Under an oxygen atmosphere of 1 atm (using an oxygen balloon), the Schlenk tube was closed and heated at 70 °C for 20 h. After cooling to room temperature, the reaction mixture was filtered. Water (10 mL) and ethyl acetate (30 mL) were added to the obtained layered solution, and then the aqueous layer was extracted with ethyl acetate (2 × 10 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated in vacuo. Further purification by column chromatography was carried out. The stationary phase of the column chromatography used was silica gel, and the eluent was a mixed solvent of petroleum ether and ethyl acetate (petroleum ether:ethyl acetate = 4:1, v / v). The yield of the target product was 43%.

[0110] The 1H NMR spectrum and 13C NMR spectrum of the obtained product are shown in Figure 13 and Figure 14 respectively, and the structure characterization data are as follows:

[0111] 1 H NMR (400 MHz, Chloroform-d) δ 8.74 (d, J = 1.7 Hz, 1H), 8.71 (d, J = 1.8 Hz, 1H), 7.96 (s, 1H), 7.83 (s, 1H), 7.66 (dd, J = 7.4, 2.0 Hz, 2H), 7.40 (d, J = 6.7 Hz, 3H), 2.53 (s, 3H);

[0112] 13 C NMR (101 MHz, Chloroform-d) δ 144.9, 144.5, 142.6, 142.0, 140.2, 139.3, 135.1, 131.4, 130.1, 129.2, 129.0, 128.2, 9.0.

[0113] HRMS (ESI): Calcd. For C 15 H 12 N2SSe [M + 1] + : 332.9966, found: 332.9964.

[0114] The selenosulfide quinoxaline compounds prepared in Examples 1 to 7 of the present invention are expected to be used in the preparation of anti-cancer, antibacterial, anti-tumor, antiviral, and anti-inflammatory drugs. For example, CN 117180276 A discloses selenated isoquinoline compounds, and their structural formula A is as follows;

[0115] This class of compounds has good anti-tumor activity.

[0116] For example, the literature (El-Atawy M A, Hamed E A, Alhadi M, et al. Synthesis and Antimicrobial Activity of Some New Substituted Quinoxalines[J]. Molecules, 2019, 24(22): 4198. DOI: 10.3390 / molecules24224198.) discloses the following compounds.

[0117] This series of compounds has antibacterial activity.

[0118] For example, the patent (CN104016931A) discloses the following compounds:

[0119] This class of compounds has good monoamine oxidase inhibitory activity.

[0120] The above has been described in detail in conjunction with the embodiments of the present invention, but the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various changes can also be made without departing from the gist of the present invention.

Claims

1. A method for preparing a selenium-sulfur-based quinoxaline compound, characterized in that, It includes the following steps: Mix the compound of formula I, the compound of formula II, the compound of formula III, a copper catalyst, an oxidant and a solvent for reaction; thus, the compound of formula IV is obtained. The structural formulas of the compound of formula I, the compound of formula II, the compound of formula III and the compound of formula IV are as follows: R1 is selected from H, C 1～12 alkyl, C 1～12 alkoxy, amino, halogen, phenyl or phenyl substituted by halogen, C 1～6 alkyl; R2 is selected from H, C 1～12 alkyl, C 1～12 alkoxy, amino, halogen, phenyl or phenyl substituted by halogen, C 1～6 alkyl.

2. The preparation method according to claim 1, characterized in that, The oxidant includes one of iodine, iodinated amine, potassium iodide, sodium persulfate, tert-butyl hydroperoxide, and bis(trifluoroacetoxy)iodobenzene.

3. The preparation method according to claim 1, wherein, The copper catalyst includes a nano copper catalyst.

4. The preparation method according to claim 3, characterized in that, The nano copper catalyst includes nano copper supported on an inorganic material.

5. The preparation method according to claim 1 or 3, characterized in that, Calculated by the molar amount of copper element, the molar ratio of the copper catalyst to the compound of formula I is 0.02 - 0.08:

1.

6. The preparation method according to claim 1, characterized in that, The molar ratio of the compound of formula I, the compound of formula II and the compound of formula III is 1:(1 - 5):(1 - 5).

7. The preparation method according to claim 1, characterized in that, The molar ratio of the oxidant to the compound of formula I is (1 - 5):

1.

8. The preparation method according to claim 1, characterized in that, The solvent is at least one of amide solvents, pyridine solvents, alcohol solvents and sulfoxide solvents.

9. The preparation method according to claim 1, characterized in that, The temperature of the reaction is 25 - 100 °C.

10. The preparation method according to claim 1, characterized in that, The time of the reaction is 1 - 24 h.

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