A method for synthesizing alkynyl compounds based on mechanical ball milling

Abstract

This invention relates to the field of organic synthesis technology, and in particular to a method for synthesizing alkynyl compounds based on mechanical ball milling. An ether compound is mixed with a compound of formula V, sodium iodide, and ethyl acetate, and then subjected to a ball milling reaction to obtain the alkynyl compound. The ball milling reaction conditions include a vibration frequency of 30 Hz and a vibration time of 30 min. This invention provides the first method to apply a mechanical strategy to the generation of alkynyl free radicals and the subsequent selenization reaction. Through ball milling-induced σ-hole sulfur bond SET, alkynyl sulfonium salts generate alkynyl free radicals and synthesize alkynyl selenides. Compared with existing technologies, the method for generating alkynyl free radicals described in this invention does not require metal catalysts or ultraviolet excitation, achieves high yields of alkynyl selenides, and features simple operation and mild reaction conditions.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a method for synthesizing alkynyl compounds based on mechanical ball milling. Background Technology

[0002] In 1887, Ostwald classified mechanochemistry, along with thermochemistry, electrochemistry, and photochemistry, as one of the four branches of chemistry based on different types of energy input (Chem. Soc. Rev., 2012, 41, 413-447). Due to its numerous advantages, including solvent-free conditions, environmental friendliness, increased reaction rates, and simpler operation, mechanochemistry has found widespread application in polymer chemistry, inorganic synthesis, and materials science. However, its application in organic synthesis has only been studied in recent decades (Science, 2019, 366, 1500-1504). Since the beginning of the 21st century, applications such as stoichiometric organic reactions like the knoevenagel condensation (Tetrahedron, 2003, 59, 3753) and metal-catalyzed reactions like the Suzuki reaction (Synth. Commun, 2000, 30, 3501-3509) have been reported. However, reports on the application of mechanochemical techniques in free radical reactions remain scarce.

[0003] Radical chemistry has gradually gained recognition as a reliable and modular approach for constructing a large number of synthetic intermediates and valuable functional molecules in the chemical, pharmaceutical, and related industries (Chem. Soc. Rev., 2018, 47, 7851). Therefore, the development of efficient methods for generating radicals has attracted considerable interest. To our knowledge, the most commonly used radical generation methods in solution chemistry are via electron transfer (ET), atom transfer (AT), and homolytic cleavage (HS) (Science, 2018, 362, 157). Electron transfer is a particularly attractive method because reactive radicals can be obtained from readily available starting materials by adding or removing electrons from the substrate (Green Chem., 2022, 24, 4557). However, existing single-electron transfer (SET) strategies for small organic molecules are mostly limited to photochemical or electrochemical transformations. In 2019, Hajime Ito and colleagues reported groundbreaking work on the realization of SET and the generation of radicals using mechanochemical techniques, providing a novel method for generating aryl groups (Science, 2019, 366, 1500-1504). More recently, Anup Bhunia and Swadhin K. Mandal described a solid-state reducing agent that activates aryl halide bonds via solid-state single-electron transfer (SSSET) under the influence of mechanical energy (Chem. Sci., 2023, 14, 2606). These studies demonstrate the enormous potential of mechanochemical strategies in the field of radical chemistry.

[0004] Compared to alkyl and aryl groups, alkynyl groups exhibit strong instability (Chem. Soc. Rev. 2011, 40, 102-113). Typical methods for generating alkynyl radicals include ultraviolet irradiation or metal catalysis (Chem. Commun., 2001, 1304-1305; Angew. Chem. Int. Ed., 2015, 54, 6046-6050). Based on our previous research, alkynyl sulfonium salts can generate alkynyl radicals via σ-hole thiobond SET under blue light (Angew. Chem. Int. Ed. 2022, 61, e202116071).

[0005] Organoselenium compounds are particularly attractive to researchers due to their ability to mimic the important biological properties of natural compounds, including antiviral, antibacterial, antitumor, and antioxidant activities. Furthermore, sulfur derivatives have been applied in the development of organic materials such as liquid crystals, organic semiconductors, and conductive polymers. Against this backdrop, developing an efficient and universal method for constructing novel Csp-Se bonds has been a challenging task (Green Chem., 2018, 20, 1560). Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a method for synthesizing alkynyl compounds based on mechanical ball milling. This method is the first to apply a mechanical strategy to the generation and selenization of alkynyl radicals. By inducing σ-hole sulfur bond SET through ball milling, alkynyl sulfonium salts generate alkynyl radicals and synthesize alkynyl selenides. This method provides a simple, efficient, and novel synthetic route for alkynyl selenides.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] This invention provides a method for synthesizing alkynyl compounds based on mechanical ball milling, comprising the following steps:

[0009] The ether compound was mixed with the compound shown in Formula V, sodium iodide, and ethyl acetate, and then subjected to ball milling to obtain an alkynyl compound.

[0010] The conditions for the ball milling reaction include: a vibration frequency of 30 Hz and a vibration time of 30 min;

[0011] The ether compound includes compounds represented by Formula III or Formula IV:

[0012]

[0013] The structural formula of the alkynyl compound is shown in Formula I or Formula II:

[0014]

[0015] In formulas III and IV, R1 is selected from unsubstituted, ortho-, meta-, or para-substituted diphenyl, dibenzyl, or dimethyl; R2 is selected from unsubstituted or para-substituted diphenyl; and R is selected from any one of unsubstituted, para-esterified or chlorinated, ortho-methyl substituted or chlorinated, or meta-chlorinated.

[0016] The structural formula of the compound shown in formula V is as follows:

[0017]

[0018] In formula V, R is selected from any one of unsubstituted, para-esterified or chlorinated, ortho-methyl substituted or chlorinated, or meta-chlorinated.

[0019] Preferably, the molar ratio of the ether compound to the compound shown in Formula V and sodium iodide is 0.036:0.9:0.072.

[0020] Preferably, the total mass ratio of the ether compound, the compound shown in Formula V, and sodium iodide to ethyl acetate is 1 mg: 0.2 μl.

[0021] Preferably, the ball milling reaction is carried out in a ball milling reactor with a volume of 1.5 ml;

[0022] The total mass of the ether compound, the compound shown in Formula V, and sodium iodide in the ball mill reactor is 55–75 mg.

[0023] Preferably, after the ball milling reaction, the resulting reactants are separated by silica gel chromatography to obtain alkynyl compounds;

[0024] The conditions for silica gel chromatography separation include: the stationary phase of column chromatography is silica, and the mobile phase is petroleum ether or a mixture thereof;

[0025] The mixture comprises petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate is 75 to 200:1.

[0026] Preferably, the volume ratio of petroleum ether to ethyl acetate is 100-150:1.

[0027] Preferably, the compound represented by Formula I is one of the compounds represented by Formula I-1 to Formula I-21:

[0028]

[0029]

[0030]

[0031] Preferably, the compound shown in Formula II is any one of the compounds shown in Formula II-1 to Formula II-10:

[0032]

[0033] The beneficial effects of this invention are as follows:

[0034] This invention provides a novel synthetic method that, for the first time, applies a mechanical strategy to the generation and selenization of alkynyl radicals. By inducing σ-hole thiobond SET through ball milling, alkynyl sulfonium salts generate alkynyl radicals and synthesize alkynyl selenides. Compared with existing technologies, the method for generating alkynyl radicals described in this invention does not require metal catalysts or UV excitation, achieves high yields of alkynyl selenides, and features simple operation and mild reaction conditions. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the embodiments will be briefly described below.

[0036] Figure 1This is a synthetic route diagram of alkynyl selenide and alkynyl telluride in a specific embodiment of the present invention. Detailed Implementation

[0037] This invention provides a method for synthesizing alkynyl compounds based on mechanical ball milling, comprising the following steps:

[0038] The ether compound was mixed with the compound shown in Formula V, sodium iodide, and ethyl acetate, and then subjected to ball milling to obtain an alkynyl compound.

[0039] The conditions for the ball milling reaction include: a vibration frequency of 30 Hz and a vibration time of 30 min;

[0040] The ether compound includes compounds represented by Formula III or Formula IV:

[0041]

[0042] The structural formula of the alkynyl compound is shown in Formula I or Formula II:

[0043]

[0044] In formulas III and IV, R1 is selected from unsubstituted, ortho-, meta-, or para-substituted diphenyl, dibenzyl, or dimethyl; R2 is selected from unsubstituted or para-substituted diphenyl; and R is selected from any one of unsubstituted, para-esterified or chlorinated, ortho-methyl substituted or chlorinated, or meta-chlorinated.

[0045] The structural formula of the compound shown in formula V is as follows:

[0046]

[0047] In formula V, R is selected from any one of unsubstituted, para-esterified or chlorinated, ortho-methyl substituted or chlorinated, or meta-chlorinated.

[0048] In this invention, the compound represented by Formula I is preferably a compound represented by Formula I-1 to Formula I-21:

[0049]

[0050]

[0051] In this invention, the compound shown in Formula II is preferably any one of the compounds shown in Formula II-1 to Formula II-10:

[0052]

[0053]

[0054] In this invention, the molar ratio of the ether compound to the compound of formula V and sodium iodide is preferably 0.036:0.9:0.072. In this invention, the volume ratio of the total mass of the ether compound, the compound of formula V, and sodium iodide to ethyl acetate is preferably 1 mg:0.2 μl. In this invention, the sodium iodide acts as an electron donor. In this invention, the ethyl acetate acts as an auxiliary grinding lubricant. In this invention, the ball milling reaction is preferably carried out in a ball mill reactor, the volume of which is preferably 1.5 ml; the total mass of the ether compound, the compound of formula V, and sodium iodide in the ball mill reactor is preferably 55–75 mg. In this invention, after the ball milling reaction, the obtained reactants are preferably separated by silica gel chromatography to obtain alkynyl compounds. The silica gel chromatography conditions preferably include: a stationary phase of silica and a mobile phase of petroleum ether or a mixture thereof; the mixture preferably includes petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is preferably 75–200:1, more preferably 100–150:1. In this invention, shortening the ball milling reaction time or reducing the oscillation frequency will lead to a decrease in yield.

[0055] To further illustrate the present invention, the following detailed description is provided in conjunction with embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0056] Example 1

[0057] The compound shown in formula I-1 is synthesized

[0058] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-1. The specific steps are as follows:

[0059] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was collected and distilled under reduced pressure to obtain the compound I-1.

[0060]

[0061] The structural verification experimental data are as follows:

[0062] colorless solid (0.039mmol, 12.5mg, >99% yield).1HNMR (500MHz, CDCl3) δ = 8.00 (d, J = 6.8Hz, 2H), 7.59 (d ,J=7.2Hz,2H),7.53(d,J=6.8Hz,2H),7.35(m,J=7.2Hz,2H),7.32-7.27(m,1H),3.92(s,3H).13C NMR (126MHz, CDCl3) δ = 166.6, 131.4, 129.8, 129.7, 129.5, 128.5, 127.9, 127.6, 103.3, 73.6, 52.4.

[0063] The obtained compound was verified to be the compound shown in Formula I-1.

[0064] Example 2

[0065] The compound shown in formula I-2 is synthesized

[0066] according to Figure 1 The synthetic route diagram shown below illustrates the synthesis of the compound represented by formula I-2. The specific steps are as follows:

[0067] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was collected and distilled under reduced pressure to obtain the compound I-2.

[0068]

[0069] The structural verification experimental data are as follows:

[0070] faint yellow solid(0.042mmol,13.8mg,>99%yield).1H NMR (500MHz, CDCl3) δ = 7.99 (d, J = 8.1Hz, 2H), 7.53-7.47 (m = 8.3Hz, 4H), 7.17 (d, J = 7.9Hz, 2H), 3.92 (s, 3H), 2.35 (s, 3H).13C NMR (126MHz, CDCl3) δ = 166.7, 137.8, 131.3, 130.6, 130.0, 129.6, 129.5, 128.0, 124.5, 101.7, 74.3, 52.4, 21.2.

[0071] The obtained compound was verified to be the compound shown in Formula I-2.

[0072] Example 3

[0073] The compound shown in formula I-3 is synthesized

[0074] according to Figure 1 The synthetic route diagram shown below synthesizes the compound represented by formula I-3. The specific steps are as follows:

[0075] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 150:1; the product was collected and distilled under reduced pressure to obtain the compound I-3.

[0076]

[0077] The structural verification experimental data are as follows:

[0078] yellow oil (0.033mmol, 12.2mg, 80% yield).1H NMR (500MHz, CDCl3): δ=7.99(d,J=8.5Hz,2H),7.56-7.49(m,4H),7.38(d,J=8.5Hz,2H),3.92(s,3H),1.32(s,9H).13C NMR (126MHz, CDCl3): δ=166.7,151.0,131.4,129.6,129.6,129.5,128.0,127.0,124.7,101.7,74.2,52.4,34.7,31.4.

[0079] Verification confirmed that the obtained compound is the compound shown in Formula I-3.

[0080] Example 4

[0081] The compound shown in formula I-4 is synthesized

[0082] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-4. The specific steps are as follows:

[0083] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was obtained by vacuum distillation after collection) to give the compound I-4.

[0084]

[0085] The structural verification experimental data are as follows:

[0086] colorless solid(0.035mmol,11.7mg,96%yield).Melting Point:77-78℃.1HNMR(500MHz, CDCl3): δ=7.98(d,J=8.3Hz,2H),7.59-7.54(m,2H),7.49(d,J=8.3Hz,2H),7.09-7.03(m,2H),3.91(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,163.6,161.7,132.0,131.9,131.4,129.7,129.7,127.7,122.7,122.7,117.1,117 .0,101.9,73.7,52.4.IR(ATR):3062,2958,2154,1710,1601,1487,1278,1107,823,766cm-1.HRMS:m / z[M]+calcd for C16H11FO2Se+:333.9903,found333.9897.

[0087] The obtained compound was verified to be the compound shown in Formula I-4.

[0088] Example 5

[0089] Synthetic compound shown in formula I-5

[0090] according to Figure 1 The synthetic route diagram shown below synthesizes the compound represented by formula I-5. The specific steps are as follows:

[0091] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was collected and distilled under reduced pressure to obtain the compound I-5.

[0092]

[0093] The structural verification experimental data are as follows:

[0094] yellow solid(0.025mmol,8.5mg,70%yield).1H NMR (500MHz, CDCl3): δ=8.04(d,J=8.3Hz,2H),7.68(d,J=8.4Hz,2H),7.61(d,J=8.4Hz,2H),7.56(d,J=8.3Hz,2H),3.94(s,3H).13C NMR (126MHz, CDCl3): δ=166.5,136.4,133.0,131.6,130.3,129.8,128.9,127.1,118.5,110.9,104.5,70.9,52.5.

[0095] The obtained compound was verified to be the compound shown in Formula I-5.

[0096] Example 6

[0097] Synthetic compound shown in formula I-6

[0098] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-6. The specific steps are as follows:

[0099] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was obtained by vacuum distillation after collection) to give the compound I-6.

[0100]

[0101] The structural verification experimental data are as follows:

[0102] yellow solid(0.038mmol,15.4mg,>99%yield).1H NMR (500MHz, CDCl3): δ = 8.01 (d, J = 8.4Hz, 2H), 7.62 (d, J = 8.8Hz, 2H), 7.53 (d, J = 8.4Hz, 2H), 7.22 (d, J = 8.8Hz, 2H), 3.93 (s, 3H).13C NMR (126MHz, CDCl3): δ = 166.6, 148.9, 131.5, 130.9, 129.9, 129.7, 127.5, 126.8, 122.4, 120.5 (q, J = 258.3Hz), 102.7, 72.8, 52.4.

[0103] The obtained compound was verified to be the compound shown in Formula I-6.

[0104] Example 7

[0105] Synthetic compound shown in formula I-7

[0106] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-7. The specific steps are as follows:

[0107] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was obtained by vacuum distillation after collection) to give the compound I-7.

[0108]

[0109] The structural verification experimental data are as follows:

[0110] yellow solid(0.036mmol,12.1mg,>99%yield).1H NMR (500MHz, CDCl3): δ=8.00(d,J=8.4Hz,2H),7.82-7.77(m,1H),7.54(d,J=8.4Hz,2H),7.23-7.18(m,3H),3.93(s,3H),2.39(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,137.0,131.4,130.5,129.8,129.7,129.2,127.9,127.6,127.5,102.4,73.5,52.4,21.2.

[0111] The obtained compound was verified to be the compound shown in Formula I-7.

[0112] Example 8

[0113] Synthetic compound I-8

[0114] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-8. The specific steps are as follows:

[0115] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was obtained by vacuum distillation after collection) to give the compound I-8.

[0116]

[0117] The structural verification experimental data are as follows:

[0118] yellow wax(0.028mmol,9.9mg,78%yield).1H NMR (500MHz, CDCl3): δ=8.04(d,J=8.3Hz,2H),7.81(d,J=7.9Hz,1H),7.58(d,J=8.3Hz,2H),7.36-7.28(m,2H),7.25-7.19(m,1H),3.93(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,131.9,131.6,130.0,129.7,129.6,129.5,129.4,128.2,128.2,127.5,104.5,72.8,52.5.

[0119] The obtained compound was verified to be the compound shown in Formula I-8.

[0120] Example 9

[0121] Synthetic compound shown in formula I-9

[0122] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-9. The specific steps are as follows:

[0123] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 75:1; the product was obtained by vacuum distillation after collection) to give the compound I-9.

[0124]

[0125] The structural verification experimental data are as follows:

[0126] faint yellow solid(0.057mmol,20.0mg,>99%yield).Melting Point:79-80℃.1H NMR (500MHz, CDCl3): δ=8.00 (d, J=8.2Hz, 2H), 7.52 (d, J=8.2Hz, 2H), 7.26-7. 23(m,1H),7.18-7.11(m,2H),6.85-6.80(m,1H),3.92(s,3H),3.82(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,160.5,131.4,130.5,129.7,129.5,127.8,121.5,114.8,113.4,102.8,73.6,55.5,52.4.

[0127] The obtained compound was verified to be the compound shown in Formula I-9.

[0128] Example 10

[0129] Synthetic compound shown in formula I-10

[0130] according to Figure 1 The synthetic route diagram shown below illustrates the synthesis of the compound represented by formula I-2. The specific steps are as follows:

[0131] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was obtained by vacuum distillation after collection) to give the compound I-10.

[0132]

[0133] The structural verification experimental data are as follows:

[0134] faint yellow solid(0.035mmol,12.4mg,98%yield).1H NMR (500MHz, CDCl3): δ=8.02(d,J=8.4Hz,2H),7.59(s,1H),7.54(d,J=8.4Hz,2H),7.48-7.42(m,1H),7.28-7.25(m,2H),3.93(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,135.6,131.5,130.7,130.2,129.9,129.7,128.9,127.7,127.5,127.2,103.3,72.5,52.4.

[0135] The obtained compound was verified to be the compound shown in Formula I-10.

[0136] Example 11

[0137] Synthetic compound shown in formula I-11

[0138] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-11. The specific steps are as follows:

[0139] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 150:1; the product was obtained by vacuum distillation after collection) to give the compound I-11.

[0140]

[0141] The structural verification experimental data are as follows:

[0142] faint yellow solid(0.043mmol,15.0mg,>99%yield).1H NMR (500MHz, CDCl3): δ = 8.01 (d, J = 8.4Hz, 2H), 7.58 (s, 1H), 7.53 (d, J = 8.4Hz, 2 H),7.08(d,J=7.7Hz,1H),7.02(d,J=7.7Hz,1H),3.92(s,3H),2.35(s,6H).13C NMR (126MHz, CDCl3): δ=166.7,137.1,134.0,131.4,130.5,130.3,129.7,129.6,128.6,128.6,128.0,102.2,73.9,52.4,21.2,20.8.

[0143] Upon verification, the obtained compound is the compound shown in Formula I-11.

[0144] Example 12

[0145] The compound shown in formula I-12 is synthesized

[0146] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-12. The specific steps are as follows:

[0147] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 150:1; the product was obtained by vacuum distillation after collection) to give the compound I-12.

[0148]

[0149] The structural verification experimental data are as follows:

[0150] yellow solid(0.027mmol,9.6mg,77%yield).1H NMR (500MHz, CDCl3): δ=8.00(d,J=8.2Hz,2H),7.52(d,J=8.2Hz,2H),7.21(s,2H),6.92(s,1H),3.92(s,3H),2.32(s,6H).13C NMR (126MHz, CDCl3): δ=166.7,139.6,131.4,129.7,129.6,129.5,128.0,127.8,127.2,102.1,74.2,52.4,21.4.

[0151] The obtained compound was verified to be the compound shown in Formula I-12.

[0152] Example 13

[0153] Synthetic compound shown in formula I-13

[0154] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-13. The specific steps are as follows:

[0155] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was obtained by vacuum distillation after collection) to give the compound I-13.

[0156]

[0157] The structural verification experimental data are as follows:

[0158] Yellow solid (0.041mmol, 15.7mg, >99% yield).1H NMR (500MHz, CDCl3): δ=8.02(d,J=8.2Hz,2H),7.67(s,1H),7.53(d,J=8.2Hz,2H),7.41(s,2H),3.93(s,3H).13C NMR (126MHz, CDCl3): δ=166.5,133.9,131.9,131.5,131.3,130.8,130.1,129.7,128.5,128.1,127.3,103.6,72.0,52.5.

[0159] The obtained compound was verified to be the compound shown in Formula I-13.

[0160] Example 14

[0161] The compound shown in formula I-14 is synthesized

[0162] according to Figure 1 The synthetic route diagram shown below illustrates the synthesis of the compound represented by formula I-2. The specific steps are as follows:

[0163] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was collected and distilled under reduced pressure to obtain the compound I-14.

[0164]

[0165] The structural verification experimental data are as follows:

[0166] Yellow solid (0.021mmol, 7.0mg, 60% yield). Melting Point: 59-60℃.1H NMR (500MHz, CDCl3): δ = 7.96 (d, J = 8.3Hz, 2H), 7.41-7.27 (m, 7H), 4.14 (s, 2H), 3.91 (s, 3H). 13C faint NMR (126MHz, CDCl3): δ=166.7,137.4,131.1,129.6,129.3,129.2,128.8,128.3,127.8,101.0,75.5,52.5 ,33.3.IR(ATR):2953,2358,2150,1717,1601,1438,1274,1109,859,760,692cm-1.HRMS:m / z[M+H]+calcd for C17H15O2Se+:331.0232,found331.0225.

[0167] Upon verification, the obtained compound is the compound shown in Formula I-14.

[0168] Example 15

[0169] Synthetic compound shown in formula I-15

[0170] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-1. The specific steps are as follows:

[0171] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was obtained by vacuum distillation after collection) to give the compound I-15.

[0172]

[0173] The structural verification experimental data are as follows:

[0174] colorless solid (0.047mmol, 12.0mg, >99% yield). Melting Point: 97-98℃. 1HNMR (500MHz, CDCl3): δ = 7.96 (d, J = 8.5Hz, 2H), 7.45 (d, J = 8.5Hz, 2H), 3.91 (s, 3H), 2.40 (s, 3H). 13C NMR (126MHz, CDCl3): δ=166.7,131.2,129.6,129.3,128.3,98.1,75.8,52.3,10.0.IR(AT R):2920,2151,1708,1599,1437,1252,1179,1111,853,768,698cm-1.HRMS:m / z[M]+calcd for C11H10O2Se+:253.9841, found 253.9829.

[0175] The obtained compound was verified to be the compound shown in Formula I-15.

[0176] Example 16

[0177] Synthetic compound shown in formula I-16

[0178] according to Figure 1 The synthetic route diagram shown below illustrates the synthesis of the compound represented by formula I-2. The specific steps are as follows:

[0179] Compound V-1 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was collected and distilled under reduced pressure to obtain the compound I-16.

[0180]

[0181] The structural verification experimental data are as follows:

[0182] faint yellow solid(0.027mmol,8.5mg,75%yield).Melting Point:123-124℃.1H NMR (500MHz, CDCl3): δ=7.98(d,J=8.3Hz,2H),7.48(d,J=8.3Hz,2H),7.46-7.44(m,1H),7.41-7.39(m,1H),7.23-7.21(m,1H),3.91(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,131.4,130.0,129.6,128.7,127.9,127.3,125.8,119.8,100.4,73.8, 52.5.IR(ATR):2952,2359,1715,1600,1434,1276,1096,848,765,693,598cm-1.HRMS:m / z[M]+calcd for C14H10O2SSe+:321.9561,found321.9555.

[0183] The obtained compound was verified to be the compound shown in Formula I-16.

[0184] Example 17

[0185] Synthetic compound shown in formula I-17

[0186] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-1. The specific steps are as follows:

[0187] Compound V-2 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 200:1; the product was obtained by vacuum distillation after collection) to give the compound I-17.

[0188]

[0189] The structural verification experimental data are as follows:

[0190] yellow oil(0.026mmol,7.5mg,75%yield).1H NMR (500MHz, CDCl3): δ=7.53(d,J=8.8Hz,2H),7.49-7.44(m,2H),7.33-7.29(m,3H),6.89(d,J=8.8Hz,2H),3.81(s,3H).13C NMR (126MHz, CDCl3): δ=159.6,132.0,131.8,128.5,128.4,123.4,118.4,115.5,101.6,70.5,55.5.

[0191] The obtained compound was verified to be the compound shown in Formula I-17.

[0192] Example 18

[0193] The compound shown in formula I-18 is synthesized

[0194] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-18. The specific steps are as follows:

[0195] Compound V-3 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 200:1; the product was collected and distilled under reduced pressure to obtain the compound I-18.

[0196]

[0197] The structural verification experimental data are as follows:

[0198] yellow wax (0.031mmol, 10.0mg, 86% yield).1H NMR (500MHz, CDCl3): δ=7.53(d,J=8.9Hz,2H),7.37(d,J=8.6Hz,2H),7.28(d,J=8.6Hz,2H),6.89(d,J=8.9Hz,2H),3.81(s,3H).13C NMR (126MHz, CDCl3): δ=159.8,134.5,133.0,132.3,128.8,121.9,118.1,115.5,100.3,72.0,55.5.

[0199] The obtained compound was verified to be the compound shown in Formula I-18.

[0200] Example 19

[0201] Synthetic compound shown in formula I-19

[0202] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-19. The specific steps are as follows:

[0203] Compound V-4 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 200:1; the product was collected and distilled under reduced pressure to obtain the compound I-19.

[0204]

[0205] The structural verification experimental data are as follows:

[0206] yellow oil(0.025mmol,8.2mg,71%yield).1H NMR (500MHz, CDCl3): δ=7.57(d,J=8.8Hz,2H),7.48-7.44(m,1H),7.39(d,J=7.7Hz,1H),7.25-7.18(m,2H),6.89(d,J=8.8Hz,2H),3.81(s,3H).13C NMR (126MHz, CDCl3): δ=159.6,135.8,133.2,131.9,129.4,129.3,126.6,123.4,118.2,115.5,98.6,76.6,55.5.

[0207] The obtained compound was verified to be the compound shown in Formula I-19.

[0208] Example 20

[0209] Synthetic compound I-20

[0210] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-20. The specific steps are as follows:

[0211] Compound V-5 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 200:1; the product was collected and distilled under reduced pressure to obtain the compound I-20.

[0212]

[0213] The structural verification experimental data are as follows:

[0214] yellow oil (0.026mmol, 8.0mg, 74% yield).1H NMR (500MHz, CDCl3): δ=7.46(d,J=7.0Hz,1H),7.24-7.20(m,3H),7.19-7.13(m,3H),6.83-6.77(m,1H),3.81(s,3H),2.48(s,3H).13C NMR (126MHz, CDCl3): δ=160.5,140.5,132.5,130.3,129.6,128.7,125.7,123.1,121.1,114.3,113.2,102.6,72.6,55.4,21.0.

[0215] The obtained compound was verified to be the compound shown in Formula I-20.

[0216] Example 21

[0217] Synthetic compound shown in formula I-21

[0218] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula I-21. The specific steps are as follows:

[0219] Compound V-6 (0.9 mmol), diselenyl ether (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 200:1; the product was collected and distilled under reduced pressure to obtain the compound I-21.

[0220]

[0221] The structural verification experimental data are as follows:

[0222] yellow oil (0.031mmol, 10mg, 86% yield).1H NMR (500MHz, CDCl3): δ = 7.46 (s, 1H), 7.36 (d, J = 7.6Hz, 1H), 7.31 (d, J = 8.1Hz, 1H),7.27-7.23(m,2H),7.15-7.11(m,2H),6.84-6.80(m,1H),3.82(s,3H).13C NMR (126MHz, CDCl3): δ=160.5,134.4,131.5,130.5,129.8,129.7,129.6,128.9,124.9,121.5,114.8,113.3,101.9,71.3,55.5.

[0223] The obtained compound was verified to be the compound shown in Formula I-21.

[0224] Example 22

[0225] The compound shown in formula II-1

[0226] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula II-1. The specific steps are as follows:

[0227] Compound V-1 (0.9 mmol), ditelluride (0.036 mmol) of Formula IV-1, and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 200:1; the product was collected and distilled under reduced pressure to obtain the compound II-1.

[0228]

[0229]

[0230] The structural verification experimental data are as follows:

[0231] faint yellow solid(0.031mmol,11.5mg,87%yield).1H NMR (500MHz, CDCl3): δ=7.99(d,J=7.9Hz,2H),7.79-7.72(m,2H),7.49(d,J=7.9Hz,2H),7.34-7.26(m,3H),3.92(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,135.7,131.7,130.0,129.8,129.6,128.4,128.0,113.7,112.9,52.4,52.1.

[0232] The obtained compound was verified to be the compound shown in Formula II-1.

[0233] Example 23

[0234] The compound shown in formula II-2

[0235] according to Figure 1 The synthetic route diagram shown below illustrates the synthesis of the compound represented by formula II-2. The specific steps are as follows:

[0236] Compound V-1 (0.9 mmol), ditelluride (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 200:1; the product was collected and distilled under reduced pressure to obtain the compound II-2.

[0237]

[0238] The structural verification experimental data are as follows:

[0239] faint yellow solid(0.036mmol,14.0mg,>99%yield).1H NMR (500MHz, CDCl3): δ=7.98(d,J=8.5Hz,2H),7.67(d,J=8.0Hz,2H),7.47(d,J=8.5Hz,2H),7.12(d,J=8.0Hz,2H),3.91(s,3H),2.36(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,138.7,136.3,131.6,130.9,129.7,129.6,128.1,113.1,108.4,52.4,52.4,21.3.

[0240] The obtained compound was verified to be the compound shown in Formula II-2.

[0241] Example 24

[0242] The compound shown in formula II-3

[0243] according to Figure 1 The synthetic route diagram shown below shows the synthesis of the compound represented by formula II-3. The specific steps are as follows:

[0244] Compound V-1 (0.9 mmol), ditelluride (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1; the product was collected and distilled under reduced pressure to obtain the compound II-3.

[0245]

[0246] The structural verification experimental data are as follows:

[0247] faint yellow solid(0.030mmol,12.0mg,84%yield).1H NMR (500MHz, CDCl3): δ=7.97(d,J=8.5Hz,2H),7.74(d,J=8.7Hz,2H),7.45(d,J=8.5Hz,2H),6.85(d,J=8.7Hz,2H),3.91(s,3H),3.81(s,3H).13C NMR (126MHz, CDCl3): δ=166.6,160.5,138.9,131.6,129.6,129.5,128.1,116.0,112.5,101.1,55.4,52.6,52.3.

[0248] The obtained compound was verified to be the compound shown in Formula II-3.

[0249] Example 25

[0250] The compound shown in formula II-4

[0251] according to Figure 1 The synthetic route diagram shown below illustrates the synthesis of the compound represented by formula II-2. The specific steps are as follows:

[0252] Compound V-1 (0.9 mmol), ditelluride (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was collected and distilled under reduced pressure to obtain the compound II-4.

[0253]

[0254] The structural verification experimental data are as follows:

[0255] faint yellow solid(0.042mmol,17.0mg,>99%yield).1H NMR (500MHz, CDCl3): δ = 8.00 (d, J = 8.4Hz, 2H), 7.68 (d, J = 8.4Hz, 2H), 7.48 (d, J = 8.4Hz, 2H), 7.27 (d, J = 8.4Hz, 2H), 3.92 (s, 3H).13C NMR (126MHz, CDCl3): δ=166.5,137.0,134.9,131.7,130.2,129.9,129.6,127.8,114.0,110.4,52.4,51.6.

[0256] The obtained compound was verified to be the compound shown in Formula II-4.

[0257] Example 26

[0258] The compound shown in formula II-5

[0259] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula II-5. The specific steps are as follows:

[0260] Compound V-1 (0.9 mmol), ditelluride (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1; the product was collected and distilled under reduced pressure to obtain the compound II-5.

[0261]

[0262] The structural verification experimental data are as follows:

[0263] yellow solid(0.046mmol,18.0mg,>99%yield).1H NMR (500MHz, CDCl3): δ=7.99(d,J=8.4Hz,2H),7.79-7.72(m,2H),7.47(d,J=8.4Hz,2H),7.05-6.98(m,2H),3.91(s,3H).13C NMR (126MHz, CDCl3): δ = 166.5, 163.4 (d, J = 248.2Hz), 138.3 (d, J = 7.6Hz), 131.7, 129.8, 129.6, 127.9, 117.4 (d, J = 21.4Hz), 113.5, 106.2 (d, J = 3.8Hz), 52.4, 51.9.

[0264] The obtained compound was verified to be the compound shown in Formula II-5.

[0265] Example 27

[0266] The compound shown in formula II-6

[0267] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula II-6. The specific steps are as follows:

[0268] Compound V-2 (0.9 mmol), ditelluride (0.036 mmol) of Formula IV-1, and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether; the product was collected and distilled under reduced pressure to obtain the compound II-6.

[0269]

[0270]

[0271] The structural verification experimental data are as follows:

[0272] yellow oil (0.032mmol, 10.0mg, 91% yield).1H NMR (500MHz, CDCl3): δ=7.74 (d, J=7.6Hz, 2H), 7.47 (d, J=7.6Hz, 2H), 7.33-7.26 (m, 6H).13C NMR (126MHz, CDCl3): δ=135.3,132.1,129.9,128.8,128.4,128.1,123.5,114.4,113.3,47.4 .IR(ATR):4048,3051,2335,2138,1571,1473,1433,1015,725,685cm-1.HRMS:m / z[M]+calcd for C14H9ClTe+:307.9839, found 307.9834.

[0273] The obtained compound was verified to be the compound shown in Formula II-6.

[0274] Example 28

[0275] The compound shown in formula II-7

[0276] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula II-7. The specific steps are as follows:

[0277] Compound V-3 (0.9 mmol), ditelluride (0.036 mmol) of Formula IV-1, and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether; the product was collected and distilled under reduced pressure to obtain the compound II-7.

[0278]

[0279] The structural verification experimental data are as follows:

[0280] colorless solid(0.035mmol,12.0mg,97%yield).Melting Point:100-101℃.1H NMR (500MHz, CDCl3): δ = 7.76-7.71 (m, 2H), 7.40-7.36 (m, 2H), 7.31-7.26 (m, 5H). 13CNMR (126MHz, CDCl3): δ = 135.5, 134.8, 133.3, 130.0 ,128.8,128.3,122.0,113.1,113.0,49.0.IR(ATR):3046,1568,1473,1433,1096,1013,833,730,690,637,532cm-1.HRMS:m / z[M]+calcd for C14H9ClTe+:341.9450,found341.9448.

[0281] The obtained compound was verified to be the compound shown in Formula II-7.

[0282] Example 29

[0283] The compound shown in formula II-8

[0284] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula II-8. The specific steps are as follows:

[0285] Compound V-6 (0.9 mmol), ditelluride (0.036 mmol) of Formula IV-1, and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether; the product was collected and distilled under reduced pressure to obtain the compound II-2.

[0286]

[0287] The structural verification experimental data are as follows:

[0288] brown oil (0.032mmol, 11.0mg, 89% yield).1H NMR (500MHz, CDCl3): δ = 7.74 (d, J = 7.4Hz, 2H), 7.43 (s, 1H), 7.30 (m, 6H). 13C NMR (126MHz, CDCl3): δ=135.6,134.2,131.8,130.1,130.0,129.6,129.0,128.3,125.2,112.9,112 .8,49.7.IR(ATR):4057,3054,2146,1555,1471,1078,870,781,679,444cm-1.HRMS:m / z[M]+calcd for C14H9ClTe+:341.9450, found 341.9445.

[0289] The obtained compound was verified to be the compound shown in Formula II-8.

[0290] Example 30

[0291] The compound shown in formula II-9

[0292] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula II-9. The specific steps are as follows:

[0293] Compound V-5 (0.9 mmol), ditelluride IV-1 (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was then added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether; the product was collected and distilled under reduced pressure to obtain the compound II-9.

[0294]

[0295] The structural verification experimental data are as follows:

[0296] yellow oil(0.037mmol,12.0mg,>99%yield).1H NMR (500MHz, CDCl3): δ=7.77-7.72(m,2H),7.43(d,J=7.6Hz,1H),7.30-7.24(m,3H),7.20(d,J=4.8Hz,2H),7.16-7.11(m,1H),2.46(s,3H).13C NMR (126MHz, CDCl3): δ=140.8,135.2,132.4,129.9,129.5,128.7,128.0,125.6,123.4,113.6,113.6, 50.8,20.9.IR(ATR):3053,2718,2135,1573,1474,1434,1016,754,727,687cm-1.HRMS:m / z[M]+calcd for C15H12Te+:321.9996,found321.9988.

[0297] The obtained compound was verified to be the compound shown in Formula II-9.

[0298] Example 31

[0299] The compound shown in formula II-10

[0300] according to Figure 1 The synthetic route diagram shown illustrates the synthesis of the compound represented by formula II-10. The specific steps are as follows:

[0301] Compound V-4 (0.9 mmol), ditelluride IV-1 (0.036 mmol), and sodium iodide (0.072 mmol) were added to a 1.5 mL ball mill reactor under air conditions. Ethyl acetate (0.2 μL / mg) was added to the mixture via a microsyringe. The reaction mixture was reacted at a vibration frequency of 30 Hz for 30 min. The reaction mixture was then transferred and separated by silica gel chromatography (stationary phase: SiO2, mobile phase: petroleum ether; the product was collected and distilled under reduced pressure to obtain the compound II-10).

[0302]

[0303] The structural verification experimental data are as follows:

[0304] yellow oil(0.029mmol,10mg,81%yield).1H NMR (500MHz, CDCl3): δ=7.78(d,J=3.5Hz,2H),7.47(d,J=8.9Hz,1H),7.40(d,J=8.9Hz,1H),7.29(s,3H),7.24-7.20(m,2H).13C NMR (126MHz, CDCl3): δ=136.2,135.3,133.6,130.0,129.6,129.4,128.1,126.5,123.4,113.2,111.2 ,53.9.IR(ATR):3052,2141,1572,1471,1434,1055,1016,751,727,685,449cm-1.HRMS:m / z[M]+calcd for C14H9ClTe+:341.9450,found 341.9449.

[0305] The obtained compound was verified to be the compound shown in Formula II-10.

[0306] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for synthesizing alkynyl compounds based on mechanical ball milling, characterized in that, Includes the following steps: The ether compound was mixed with the compound shown in Formula V, sodium iodide, and ethyl acetate, and then subjected to ball milling to obtain an alkynyl compound. The conditions for the ball milling reaction include: a vibration frequency of 30 Hz and a vibration time of 30 min; The ether compound includes compounds represented by Formula III or Formula IV: Formula III Formula IV The structural formula of the alkynyl compound is shown in Formula I or Formula II: Formula I Formula II In formulas III and IV, R1 is selected from unsubstituted, ortho-, meta-, or para-substituted phenyl, benzyl, or methyl; R2 is selected from unsubstituted or para-substituted phenyl; and R is selected from any one of unsubstituted, para-esterified or chlorinated, ortho-methyl substituted or chlorinated, or meta-chlorinated. The structural formula of the compound shown in formula V is as follows: Formula V In formula V, R is selected from any one of unsubstituted, para-esterified or chlorinated, ortho-methyl substituted or chlorinated, or meta-chlorinated.

2. The synthesis method according to claim 1, characterized in that, The molar ratio of the ether compound to the compound shown in Formula V and sodium iodide is 0.036:0.9:0.

072.

3. The synthesis method according to claim 1, characterized in that, The total mass ratio of the ether compound, the compound shown in Formula V, and sodium iodide to ethyl acetate is 1 mg: 0.2 µl.

4. The synthesis method according to claim 1, characterized in that, The ball milling reaction is carried out in a ball milling reactor with a volume of 1.5 ml; The total mass of the ether compound, the compound shown in Formula V, and sodium iodide in the ball mill reactor is 55~75 mg.

5. The synthesis method according to claim 1, characterized in that, After the ball milling reaction, the resulting reactants were separated by silica gel chromatography to obtain alkynyl compounds; The conditions for silica gel chromatography separation include: the stationary phase of column chromatography is silica, and the mobile phase is petroleum ether or a mixture thereof; The mixture comprises petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate is 75~200:

1.

6. The synthesis method according to claim 5, characterized in that, The volume ratio of petroleum ether to ethyl acetate is 100~150:

1.

7. The synthesis method according to claim 1, characterized in that, The compound represented by Formula I is the compound shown in Formula I-1 to Formula I-21 below: Formula I-1 Formula I-2 Formula I-3 Formula I-4 Formula I-5 Formula I-6 Formula I-7 Formula I-8 Formula I-9 Formula I-10 Formula I-11 Formula I-12 Formula I-13 Formula I-14 Formula I-15 Formula I-16 Formula I-17 Formula I-18 Formula I-19 Formula I-20 Formula I-21.

8. The synthesis method according to claim 1, characterized in that, The compound shown in Formula II is any one of the compounds shown in Formula II-1 to Formula II-10 below: Formula II-1 Formula II-2 Formula II-3 Formula II-4 Formula II-5 Formula II-6 Formula II-7 Formula II-8 Formula II-9 Formula II-10.

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