Method for synthesizing aromatic thioether and selenide compound through neutral sulfur bond strategy

Abstract

The invention discloses a method for synthesizing aromatic thioether and selenide compounds through a neutral sulfur bond strategy. The method comprises the following steps: under the irradiation of blue light, in a specific solvent, reacting a compound shown as a formula III with a compound shown as a formula IV or a compound shown as a formula V in an inert atmosphere to obtain a compound shown as a formula I or a compound shown as a formula II. According to the method disclosed by the invention, various aromatic thioether and selenide compounds are synthesized under the action of light by adopting a brand-new catalytic mode, namely neutral sulfur bonds, and a simple, efficient, economical and green way is provided for synthesis of the aromatic thioether and selenide compounds. # imgabs0 # imgabs1 #

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and in particular relates to the synthesis of aromatic thioether and selenoether compounds through a neutral sulfur bond strategy. Background Art

[0002] Aromatic sulfides and selenoethers are widely used in chemical and pharmaceutical research and have attracted great interest ( Bioorg. Med. Chem. Lett. 2013, 23, 4669–4673, J. Med. Chem. 2022, 65, 4436–4456.). Subsequently, many methods for constructing CS / Se bonds emerged ( Chem. Rev. 2014, 114, 8807–8864; Chem. Soc. Rev. 2015, 44, 291–314). Common methods include transition metal and photoredox-mediated cross-coupling of aryl halides with thiolates / selenides. However, these methods usually rely on transition metals, t Strong bases such as BuOK and the use of toxic and malodorous thiols / selenols as precursors of RS / Se- anions. In addition, the scope of substrates is usually limited to aromatic derivatives ( J. Am. Chem. Soc. 2017, 139, 13616–13619; Angew. Chem. Int. Ed. 2019,58, 5033–5037). Despite some progress, the cross-coupling of aryl halides with thiolates / selenides remains a problem. These problems include the development of new chalcogenides as R-Ch under metal-free and strong base conditions. - Anion precursors, as well as the presence of aryl radicals and thiols / selenates, can suggest reliable pathways.

[0003] Sulfide bonds (ChBs) are σ-hole-directed interactions with many potential advantages, such as high directionality, tunability, and multiplicity ( J. Am. Chem. Soc. 2017, 139, 15160–15167; J. Am. Chem. Soc. 2021,143, 8625–8630). In addition, since its binding strength can be easily modified, it is able to create new activation modes for various transformations. Currently, most studies have focused on cationic ChBs, while studies on neutral ChBs are scarce. Therefore, we envision that exploring effective methods to utilize neutral ChBs in substrate activation can expand the potential of ChBs in organic transformations by introducing new activation modes or pathways.

[0004] In summary, the current methods for synthesizing aromatic sulfides and selenoethers use transition metals, strong bases such as tBuOK, and toxic and smelly thiols / selenols as precursors, which are insufficient in terms of economy and environmental protection. Therefore, it is imperative to develop new, economical, and green methods for synthesizing aromatic sulfides and selenoethers. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a method for synthesizing aromatic sulfides and selenoethers through a neutral sulfur bond strategy. The method adopts a new catalytic mode - neutral sulfur bond, and synthesizes various aromatic sulfides and selenoether compounds under the action of light. The method provides a simple, efficient, economical and green way for the synthesis of aromatic sulfides and selenoether compounds.

[0006] The present invention provides a method for synthesizing an aromatic sulfide and a selenoether compound, wherein the structural formulas of the aromatic sulfide and the selenoether compound are as shown in Formula I and Formula II:

[0007] In formula I and II, R1 and R2 represent substituents on the benzene ring, which may be monosubstituted or polysubstituted, and are independently selected from: H, deuterium, C1-C 10 Alkyl (such as C1-C6 alkyl), C1-C 10 Any of alkoxy (such as C1-C6 alkoxy), halogen, cyano, and ester; The method for synthesizing aromatic sulfide and selenoether compounds provided by the present invention comprises the following steps: Under blue light irradiation, the compound represented by formula III undergoes a free radical addition reaction with the compound represented by formula IV or the compound represented by formula V in an inert atmosphere to obtain a compound represented by formula I or formula II;

[0008] In Formula III, R2 represents a substituent on the benzene ring, which may be a single or multiple substitution, each independently selected from: H, deuterium, C1-C 10 Alkyl (such as C1-C6 alkyl), C1-C 10 Any of alkoxy (such as C1-C6 alkoxy), halogen, cyano, and ester; In formula IV and V, R1 represents a substituent on the benzene ring, which may be monosubstituted or polysubstituted, each independently selected from: H, deuterium, C1-C 10 Alkyl (such as C1-C6 alkyl), C1-C 10 Any of alkoxy (e.g. C1-C6 alkoxy), halogen, cyano, and ester.

[0009] As an example, the compound represented by formula I is a compound represented by formula I-1 to a compound represented by formula I-4:

[0010] As an example, the compound represented by formula II is a compound represented by formula II-1 to a compound represented by formula II-8:

[0011] In the above synthesis method, the molar ratio of the compound represented by formula III to the compound represented by formula IV or the compound represented by formula V can be 2-4:1, specifically 4:1; The free radical addition reaction is carried out in the presence of an organic base. The organic base may be at least one of TMTAC, Et3N, DIPEA, TMEDA, and Cy2NMe, and may specifically be TMTAC; The molar ratio of the organic base to the compound represented by formula III is 1-2:1.

[0012] The reaction is carried out in an organic solvent, and the organic solvent may specifically be MeCN.

[0013] In the above synthesis method, the concentration of the compound represented by Formula IV or the compound represented by Formula V in the MeCN solvent may be 0.1-0.2M, specifically 0.2M.

[0014] In the above synthesis method, the wavelength of the blue light may be 450nm; the blue light may be provided by a blue LED lamp, and the power of the LED lamp may be 100W.

[0015] In the above synthesis method, the temperature of the free radical addition reaction can be 65-75° C. (specifically 70° C.), and the time can be 8-12 h, specifically 12 h.

[0016] In the above-mentioned synthesis method, the method also includes the steps of silica gel chromatography separation of the system after the reaction is completed, and vacuum distillation after collection; preferably, the stationary phase of the silica gel chromatography separation is SiO2; and the mobile phase is a mixture of petroleum ether and ethyl acetate.

[0017] Compared with the prior art, the technical solution of the present invention has the following advantages: The method of the present invention adopts neutral sulfur bond catalysis for the first time to prepare aromatic sulfide and selenoether compounds under the action of light. Compared with the prior art, the synthesis method of aromatic sulfide and selenoether compounds of the present invention has the characteristics of mild reaction conditions, economy, and greenness. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The present invention provides a synthetic route for the aromatic sulfide and selenoether compounds. DETAILED DESCRIPTION

[0019] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.

[0020] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial channels.

[0021] Example 1: Synthesis of the compound represented by formula I-1 according to Figure 1 The compound of formula Ⅰ-1 is synthesized according to the synthetic route shown in the figure. The specific steps are as follows: The pre-dried reaction tube was added with the compound of formula III-1 (0.8 mmol), the compound of formula IV-1 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) under 100W blue LED (450 nm) lamp at 70°C. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound of formula I-1.

[0022]

[0023] The experimental data of structure verification are as follows: white solid (28.9 mg, 0.134 mmol, 67%). 1 H NMR (500 MHz, CDCl3) δ 7.47 –7.37 (m, 2H), 7.27 – 7.20 (m, 2H), 7.18 – 7.09 (m, 2H), 6.99 – 6.85 (m, 2H), 3.82 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 159.9, 138.7, 135.6, 129.1, 128.2, 125.9, 124.3, 115.1, 55.5. It was verified that the obtained compound was the compound represented by formula I-1.

[0024] Example 2: Synthesis of the compound represented by formula I-2 according to Figure 1 The compound of formula I-2 is synthesized according to the synthetic route shown in the figure, and the specific steps are as follows: The pre-dried reaction tube was added with the compound of formula III-2 (0.8 mmol), the compound of formula IV-2 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) at 70°C under a 100W blue LED (450 nm) lamp. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound of formula I-2.

[0025]

[0026] The experimental data of structure verification are as follows: white solid (26.2 mg, 0.112 mmol, 56%). 1 H NMR (400 MHz, CDCl3) δ 7.32 –7.26 (m, 2H), 7.16 – 7.09 (m, 2H), 6.92 – 6.86 (m, 2H), 6.84 – 6.78 (m, 2H), 3.74 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 161.8 (d, J = 245.9 Hz), 159.8, 134.6,133.3 (d, J = 3.3 Hz), 131.2 (d, J = 7.9 Hz), 125.4, 116.2 (d, J = 22.0 Hz), 115.2,55.5. It was verified that the obtained compound was the compound represented by formula I-2.

[0027] Example 3: Synthesis of the compound represented by formula I-3 according to Figure 1 The compound of formula I-3 is synthesized according to the synthetic route shown in the figure, and the specific steps are as follows: The pre-dried reaction tube was added with the compound represented by formula III-3 (0.8 mmol), the compound represented by formula IV-2 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) under 100W blue LED (450 nm) lamp at 70°C. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, volume ratio, and the product was obtained by vacuum distillation after collection), to obtain the compound represented by formula I-3.

[0028]

[0029] The experimental data of structure verification are as follows: white solid (25.0 mg, 0.100 mmol, 50%). 1 H NMR (600 MHz, CDCl3) δ 7.40 –7.34 (m, 2H), 7.07 (t, J = 7.8 Hz, 1H), 7.04 – 6.98 (m, 2H), 6.94 – 6.91 (m,1H), 6.89 – 6.83 (m, 2H), 3.77 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 160.5, 141.5, 136.3, 134.9, 130.0, 127.2, 125.7, 125.6, 122.8, 115.4, 55.5. It was verified that the obtained compound was the compound represented by formula I-3.

[0030] Example 4: Synthesis of the compound represented by formula I-4 according to Figure 1 The compound of formula I-4 is synthesized according to the synthetic route shown in the figure, and the specific steps are as follows: The pre-dried reaction tube was added with the compound represented by formula III-6 (0.8 mmol), the compound represented by formula IV-1 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) under 100W blue LED (450 nm) lamp at 65-75°C. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, and the product was obtained by vacuum distillation after collection) to obtain the compound represented by formula I-4.

[0031]

[0032] The experimental data of structure verification are as follows: white solid (28.5 mg, 0.124 mmol, 62%). 1 H NMR(400 MHz, CDCl3) δ 7.36 –7.27 (m, 2H), 7.25 – 7.20 (m, 2H), 7.20 – 7.09 (m, 3H), 6.81 (d, J = 8.4 Hz,1H), 3.84 (s, 3H), 2.19 (s, 3H). 13 C NMR(101 MHz, CDCl3) δ 158.3, 139.1, 136.5,133.2, 129.0, 128.2, 128.0, 125.7, 123.4, 110.8, 55.5, 16.3. It was verified that the obtained compound was the compound represented by formula I-4.

[0033] Example 5: Synthesis of the compound represented by formula II-1 according to Figure 1 The compound shown in formula II-1 is synthesized according to the synthetic route shown in the figure. The specific steps are as follows: The pre-dried reaction tube was added with the compound of formula III-1 (0.8 mmol), the compound of formula V-1 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) at 70°C under a 100W blue LED (450 nm) lamp. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound of formula II-1.

[0034]

[0035] The experimental data of structure verification are as follows: yellow liquid (35.4 mg, 0.134 mmol, 67%). 1H NMR(500 MHz, CDCl3) δ 7.56– 7.47 (m, 2H), 7.37 – 7.30 (m, 2H), 7.24 – 7.15 (m, 3H), 6.90 – 6.81 (m,2H), 3.81 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 158.9, 135.7, 132.3, 130.0, 128.3, 125.6, 119.1, 114.3, 54.4. It was verified that the obtained compound was the compound represented by formula II-1.

[0036] Example 6: Synthesis of the compound represented by formula II-2 according to Figure 1 The compound shown in formula II-2 is synthesized according to the synthetic route shown in the figure, and the specific steps are as follows: The pre-dried reaction tube was added with the compound represented by formula III-2 (0.8 mmol), the compound represented by formula V-2 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) at 70°C under a 100W blue LED (450 nm) lamp. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100:1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound represented by II-2.

[0037]

[0038] The experimental data of structure verification are as follows: white solid (44.0 mg, 0.156 mmol, 78%). 1 H NMR (500 MHz, CDCl3) δ 7.49 –7.44 (m, 2H), 7.38 – 7.32 (m, 2H), 6.98 – 6.90 (m, 2H), 6.88 – 6.81 (m, 2H), 3.80 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 161.2 (d, J = 246.3 Hz), 158.9, 135.0,132.7 (d, J = 7.8 Hz), 126.4 (d, J= 3.3 Hz), 119.7, 115.5 (d, J = 21.6 Hz), 114.3,54.5. It was verified that the obtained compound was the compound represented by formula II-2.

[0039] Example 7: Synthesis of the compound represented by formula II-3 according to Figure 1 The compound shown in the synthetic route is synthesized according to formula II-3, and the specific steps are as follows: The pre-dried reaction tube was added with the compound represented by formula III-3 (0.8 mmol), the compound represented by formula V-2 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) at 70°C under a 100W blue LED (450 nm) lamp. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound represented by formula II-1.

[0040]

[0041] The experimental data of structure verification are as follows: white solid (42.9 mg, 0.144 mmol, 72%).Melting point: 130 – 131 ℃. 1 HNMR(500 MHz, CDCl3) δ 7.56 – 7.49 (m, 2H), 7.25 – 7.23 (m, 1H), 7.17 – 7.09(m, 3H), 6.94 – 6.85 (m, 2H), 3.82 (s, 3H). 13 C NMR(126 MHz, CDCl3) δ 160.3,137.4, 135.6, 135.0, 130.2, 129.9, 128.3, 126.5, 118.8, 115.5, 55.5.IR (ATR):1612, 1523, 1292, 1135, 1066, 754, 688cm -1 .HRMS: m / z: [M+Na] + calcd.forC 13 H 11 ClOSeNa +: 320.9556 found 320.9557. It was verified that the obtained compound was the compound represented by formula II-3.

[0042] Example 8: Synthesis of the compound represented by formula II-4 according to Figure 1 The compound shown in formula II-4 is synthesized according to the synthetic route shown in the figure, and the specific steps are as follows: The pre-dried reaction tube was added with the compound represented by formula III-4 (0.8 mmol), the compound represented by formula V-2 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) at 70°C under a 100W blue LED (450 nm) lamp. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 40: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound represented by formula II-4.

[0043]

[0044] The experimental data of structure verification are as follows: white solid (36.7 mg, 0.114 mmol, 57%). 1 H NMR (500 MHz, CDCl3) δ 7.88 –7.78 (m, 2H), 7.62 – 7.51 (m, 2H), 7.31 – 7.20 (m, 2H), 6.95 – 6.88 (m, 2H), 3.87 (s, 3H), 3.83 (s, 3H). 13 C NMR(126 MHz, CDCl3) δ 167.0, 160.5, 141.6,137.9, 130.1, 128.9, 127.7, 118.0, 115.5, 55.4, 52.2. It was verified that the obtained compound was the compound represented by formula II-4.

[0045] Example 9: Synthesis of the compound represented by formula II-5 according to Figure 1 The compound shown in the synthetic route is synthesized according to formula II-5, and the specific steps are as follows: The pre-dried reaction tube was added with the compound represented by formula III-5 (0.8 mmol), the compound represented by formula V-2 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) at 70°C under a 100W blue LED (450 nm) lamp. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 40: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound represented by formula II-5.

[0046]

[0047] The experimental data of structure verification are as follows: yellow solid (35.6 mg, 0.128 mmol, 64%). 1 H NMR (500 MHz, CDCl3) δ 7.63– 7.55 (m, 3H), 7.35 – 7.30 (m, 1H), 7.25 – 7.20 (m, 1H), 7.11 (d, J = 8.0 Hz,1H), 7.01 – 6.88 (m, 2H), 3.84 (s, 3H). 13 C NMR(126 MHz, CDCl3) δ 160.8, 139.6,138.2, 133.7, 133.0, 130.8, 126.4, 117.7, 117.5, 115.7, 113.5, 55.5. It was verified that the obtained compound was the compound represented by formula II-5.

[0048] Example 10: Synthesis of the compound represented by formula II-6 according to Figure 1 The compound shown in the synthetic route is synthesized according to formula II-6, and the specific steps are as follows: The pre-dried reaction tube was added with the compound represented by formula III-6 (0.8 mmol), the compound represented by formula V-1 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) under 100W blue LED (450 nm) lamp at 70°C. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound represented by formula II-6.

[0049]

[0050] The experimental data of structure verification are as follows: yellow liquid (36.7 mg, 0.132 mmol, 66%). 1 H NMR (500 MHz, CDCl3) δ 7.43– 7.36 (m, 2H), 7.34 – 7.30 (m, 2H), 7.24 – 7.11 (m, 3H), 6.77 (d, J = 8.4 Hz,1H), 3.83 (s, 3H), 2.19 (s, 3H). 13 C NMR(126 MHz, CDCl3) δ 158.2, 137.7, 134.3,133.6, 130.8, 129.2, 128.3, 126.4, 119.3, 111.0, 55.5, 16.2.IR (ATR): 1576,1487, 1241, 1133, 1029, 804, 732cm -1 .HRMS: m / z: [M] calcd. for C 14 H 14 OSe:278.0204 found 278.0205. It was verified that the obtained compound was the compound represented by formula II-6.

[0051] Example 11, Synthesis of the compound represented by formula II-7 according to Figure 1 The compound shown in the synthetic route is synthesized according to formula II-7, and the specific steps are as follows: The pre-dried reaction tube was added with the compound of formula III-7 (0.8 mmol), the compound of formula V-3 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) at 70°C under a 100W blue LED (450 nm) lamp. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound of formula II-7.

[0052]

[0053] The experimental data of structure verification are as follows: yellow liquid (48.6 mg, 0.142 mmol, 71%). 1 H NMR (600 MHz, CDCl3) δ 7.41– 7.36 (m, 2H), 7.34 – 7.29 (m, 2H), 7.20 (t, J = 8.0 Hz, 1H), 7.06 – 7.01 (dt, J = 7.7, 1.2 Hz, 1H), 7.00 (t, J = 2.0 Hz, 1H), 6.82 (dd, J = 8.3, 2.6 Hz, 1H), 3.77 (s, 3H). 13 C NMR(151 MHz, CDCl3) δ 160.2, 134.6, 132.6, 131.6, 130.4,130.2, 125.5, 121.8, 118.6, 113.6, 55.5.IR (ATR): 2078, 1896, 1584, 1242,1227, 1066, 1004, 805 cm -1 .HRMS: m / z: [M] calcd. for C 13 H 11 BrOSe: 341.9153 found 341.9150. It was verified that the obtained compound was the compound represented by formula II-7.

[0054] Example 12: Synthesis of the compound represented by formula II-8 according to Figure 1 The compound shown in the synthetic route is synthesized according to formula II-8, and the specific steps are as follows: The pre-dried reaction tube was added with the compound represented by formula III-7 (0.8 mmol), the compound represented by formula V-4 (0.2 mmol), TMTAC (0.8 mmol), and MeCN (1.0 mL) under nitrogen protection, and stirred overnight (12 h) at 70°C under a 100W blue LED (450 nm) lamp. The reaction mixture was then subjected to vacuum distillation and silica gel chromatography separation (column chromatography stationary phase: SiO2, mobile phase: petroleum ether / ethyl acetate = 100: 1, volume ratio, and the product was obtained by vacuum distillation after collection) to obtain the compound represented by formula II-8.

[0055]

[0056] The experimental data of structure verification are as follows: yellow liquid (39.1 mg, 0.132 mmol, 66%). 1 H NMR(500 MHz, CDCl3) δ 7.45(dd, J = 8.5, 6.0 Hz, 1H), 7.15 (t, J = 8.0 Hz, 1H), 6.99 (dd, J = 9.6, 2.9 Hz,1H), 6.90 – 6.79 (m, 3H), 6.78 – 6.73 (m, 1H), 3.74 (s, 3H), 2.40 (s, 3H). 13 CNMR(126 MHz, CDCl3) δ 163.1 (d, J = 247.5 Hz), 160.2, 143.7 (d, J = 7.9 Hz),137.2 (d, J = 8.2 Hz), 132.7, 130.2, 125.4 (d, J = 3.1 Hz), 123.7, 117.4 (d, J =21.3 Hz), 116.8, 114.0 (d, J = 21.1 Hz), 112.6, 55.4, 23.0.IR (ATR): 1585,1469, 1273, 1066, 943, 861, 766, 683 cm -1 .HRMS: m / z: [M] calcd. for C 14 H 13 FOSe:296.0110 found 296.0111. It was verified that the obtained compound was the compound represented by formula II-8.

[0057] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, and without the need to carry out unnecessary experimental conditions, the present invention can be implemented in a wide range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principles of the present invention, the application is intended to include any changes, uses or improvements to the present invention, including departure from the disclosed scope in the application, and changes made with conventional techniques known in the art.

Claims

1. A method for synthesizing aromatic sulfide and selenoether compounds, wherein: The structural formulas of the aromatic sulfide and selenoether compounds are shown in Formula I and Formula II: In formula I and II, R1 and R2 represent substituents on the benzene ring, which are monosubstituted or polysubstituted, and are independently selected from: H, deuterium, C1-C 10 Alkyl, C1-C 10 Any of alkoxy, halogen, cyano, and ester groups; The steps include: Under blue light irradiation, the compound represented by formula III undergoes a free radical addition reaction with the compound represented by formula IV or the compound represented by formula V in an inert atmosphere to obtain a compound represented by formula I or formula II; In Formula III, R2 represents a substituent on the benzene ring, which is a single or multiple substitution, each independently selected from: H, deuterium, C1-C 10 Alkyl, C1-C 10 Any of alkoxy, halogen, cyano, and ester groups; In formula IV and V, R1 represents a substituent on the benzene ring, which is a single or multiple substitution, each independently selected from: H, deuterium, C1-C 10 Alkyl, C1-C 10 Any of alkoxy, halogen, cyano and ester groups.

2. The method according to claim 1, characterized in that In the synthesis method, the molar ratio of the compound represented by formula III to the compound represented by formula IV or the compound represented by formula V is 2-4:1; The free radical addition reaction is carried out in the presence of an organic base. The organic base is at least one of TMTAC, Et3N, DIPEA, TMEDA and Cy2NMe; The molar ratio of the organic base to the compound represented by formula III is 1-2:

1.

3. The method according to claim 1, characterized in that In the synthesis method, the wavelength of the blue light is 450nm; the blue light is provided by a blue LED lamp, and the power of the LED lamp is 100W.

4. The method according to claim 1, characterized in that In the synthesis method, the temperature of the free radical addition reaction is 65-75° C. and the time is 8-12 hours.

5. The method according to claim 1, characterized in that The reaction is carried out in an organic solvent, and the organic solvent is specifically MeCN; The concentration of the compound represented by formula IV or the compound represented by formula V in MeCN solvent is 0.1-0.2M.

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