Method for synthesizing aryl thioether compound

Abstract

The invention belongs to the technical field of synthesis of thioether compounds, and particularly discloses a method for synthesizing aryl thioether compounds. According to the method, the aryl sulfinic acid sodium salt and the aryl iodide are adopted as reaction raw materials, the Cu / MSilicalite-1 zeolite is adopted as the catalyst, the aryl thioether compound is obtained through the reaction in the air atmosphere, the adopted sulfur source is non-toxic, odorless and not prone to volatilization, the reaction condition is mild, the reaction efficiency is high, the Cu / MSilicalite-1 zeolite has good chemical stability and recoverability, and the method is suitable for industrial production. The product yield is good, basically no by-product is generated, the substrate expansibility is wide, and the method has economic value and industrial significance.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthetic chemistry, and specifically relates to a reaction for synthesizing aryl sulfide compounds by taking aryl sulfinic acid sodium salt and aryl iodide as reaction raw materials under the action of Cu / MSilicalite-1 zeolite. Background Art

[0002] Aryl sulfide derivatives are an important class of basic organic compounds. As intermediates in organic synthesis and drug synthesis, they are widely used in the fields of medicine, pesticides, and chemicals. This type of compound is an important pharmacophore in the structure of many drugs and is very common in anti-inflammatory, anti-cancer, anti-AIDS therapeutic drugs and Alzheimer's, asthma, and Parkinson's disease therapeutic drug molecules. In view of the importance of aromatic sulfides, various methods have been developed, such as cross-coupling of aromatic halides or aromatic boronic acids with sulfiding agents (thiols, disulfides, sulfonyl hydrazides, etc.) (Org. Biomol. Chem., 2017, 15(9): 1942-1946.), CH bond functionalization using thiols or disulfides as sulfiding agents ([J]. JActa Phys.-Chim. Sin 2019, 35(9): 954-967.), nucleophilic substitution reaction in alkaline medium (Organic Letters 2010, 12(10): 2430-2433.), and desulfurization of aromatic disulfides ([J]. Tetrahedron, 2017, 73(26): 3702-3706). Among these reports, the cross-coupling of aryl halides with sulfiding agents has received great attention and has been extensively studied due to the fact that it does not require tedious processes for substrate pre-functionalization or preparation of ligands, as well as a wide substrate scope. However, there are several challenges in using thiols as sulfiding agents: malodor, high volatility, and more importantly, oxidative sulfur-sulfur coupling of thiols easily occurs, leading to the formation of undesirable disulfide byproducts.

[0003] Therefore, it is urgent to develop an efficient, green, and pollution-free sulfiding agent for the synthesis of aromatic sulfide compounds. In this patent, a method for synthesizing aromatic sulfide compounds using salt compounds as sulfiding agents and zeolite as reaction catalysts is developed. Compared with other routes, this method greatly improves the yield of sulfide compounds under the premise of environmental protection and low cost. Summary of the invention

[0004] The invention provides a method for simply synthesizing an aryl sulfide compound, and realizes the arylsulfidation reaction of sodium benzenesulfinate and iodobenzene under the catalytic action of Cu / MSilicalite-1 zeolite.

[0005] The characteristics of the present invention are: ① the sulfur source is non-toxic, odorless and non-volatile; ② the reaction conditions are mild and the reaction efficiency is high; ③ the Cu / MSilicalite-1 zeolite has good chemical stability and recyclability; ④ the product yield is good and basically no by-products are generated; ⑤ the substrate has wide expansibility

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] Aryl sulfinic acid sodium salt and aryl iodide compounds are added as reaction raw materials into a reaction container, and Cu / MSilicalite-1 zeolite and a reaction solvent are added. After reacting for a certain period of time in an air atmosphere, the reaction liquid is extracted, centrifuged, and rotary evaporated by conventional separation means, and the separated system is separated by silica gel column chromatography to obtain pure aryl sulfide compounds.

[0008] The reaction structure is as follows:

[0009]

[0010] R1 is selected from hydrogen, amino, alkyl, halogen, alkoxy, aryl or substituted aryl.

[0011] Furthermore, R1 is selected from one of hydrogen, 4-amino, 4-methyl, 4-ethyl, 4-bromo, 2-fluoro, 4-fluoro, 1,3-dimethyl, and 4-phenyl.

[0012] The reaction temperature in the present invention is 100-160°C.

[0013] The reaction time in the present invention is 1 to 5 hours.

[0014] The reaction solvent in the present invention may be one of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) and 1,4-dioxane.

[0015] Furthermore, the molar ratio of the arylsulfinic acid sodium salt to the aryl iodide is 5:1 to 1:1, preferably 3:1 to 1:1.

[0016] Furthermore, the source of MSilicalite zeolite is not limited. Mesoporous MSilicalite zeolite is preferred, which is more conducive to the reaction. The specific surface area and other parameters of MSilicalite with mesoporous structure are as follows: the specific surface area is 350-450m 2 / g, and the mesopore volume is 0.1~0.20cm 3 / g, with an external surface area of ​​100 to 180 m 2 / g, micropore volume is 0.09~0.16cm 3 / g.

[0017] The copper loading in the Cu / MSilicalite-1 zeolite is 1% to 10%, preferably 3% to 7%, and can be prepared by a conventional equal volume impregnation method.

[0018] Furthermore, the molar amount of the aryl iodide and the mass ratio of Cu / MSilicalite-1 zeolite is 1:100 to 1:200 mol / g, preferably 1:120 to 1:170 mol / g.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The sulfur source is non-toxic, odorless, and non-volatile. The reaction conditions are simple, the operation is simple, the reaction conditions are mild, and the reaction yield is high.

[0021] (2) The Cu / MSilicalite-1 catalyst is easy to separate and recycle, can be reused many times, has good stability, and has economic value and industrial significance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The diphenyl sulfide obtained in Example 1 1 H-NMR spectrum.

[0023] Figure 2 The 4-methyl diphenyl sulfide obtained in Example 5 1 H-NMR spectrum.

[0024] Figure 3 The 2-aminodiphenyl sulfide obtained in Example 6 1 H-NMR spectrum.

[0025] Figure 4 is the (2-fluorophenyl)(phenyl)sulfane obtained in Example 7 1 H-NMR spectrum.

[0026] Figure 5 The 4-bromodiphenyl sulfide obtained in Example 8 1 H-NMR spectrum.

[0027] Figure 6 The 4-fluorodiphenyl sulfide obtained in Example 9 1 H-NMR spectrum.

[0028] Figure 7 1,3-dimethyl-5-(phenylthio)benzene obtained in Example 10 1 H-NMR spectrum.

[0029] Figure 8 The 4-(phenylthio)-1,1'-biphenyl obtained in Example 111 H-NMR spectrum.

[0030] Fig. 9 1,3-dichloro-5-benzylthiobenzene obtained in Example 12 1 H-NMR spectrum. DETAILED DESCRIPTION

[0031] In order to further understand the purpose, content and advantages of the present invention, the specific embodiments of the present invention are described in detail below, but they are not limited to the following examples, and the reaction conditions should be changed according to the actual situation. Unless otherwise specified, the reagents and instruments used in the following examples are all commercially available products.

[0032] The Silicalite-1 zeolite used in the embodiment was prepared according to the previous work of this group. The specific preparation method is as follows: first, 11.6 mL of 25% tetraethylammonium hydroxide (TPAOH) was slowly dripped into 14.4 mL of tetraethyl silicate (TEOS), stirred for 0.5 h, 9.6 mL of water was added, stirred for 1 h, and heated in a 75°C water bath (open) for 5 h to obtain a transparent solution, 4.4 mL of an organic quaternary ammonium salt (DM3015N of Demei Chemical) was added, and stirred for 1 h. The transparent solution was transferred to a 50 L autoclave for dynamic crystallization and stored at 180°C for 3 days. The solid product was filtered, dried, and calcined at 550°C for 4 h to remove the organic template.

[0033] The specific preparation process of Cu / MSilicalite-1 is as follows: 0.1133 g of copper nitrate was weighed and dissolved in an appropriate amount of distilled water to prepare a copper nitrate metal salt solution, which was added dropwise to 1.0 g of MSilicalite zeolite by an equal volume impregnation method. After drying at room temperature for 12 h, it was placed in an oven at 100 °C for 8 h and calcined in a muffle furnace under air atmosphere. The calcination procedure was: 5 °C·min -1 The temperature was raised from room temperature to 100°C at a rate of 3°C·min -1 The temperature was increased from 100°C to 550°C at a rate and maintained for 4 hours to obtain Cu / MSilicalite-1 zeolite catalyst.

[0034] Embodiment 1:

[0035]

[0036] A 10mL Schlenk reaction tube was used as the container of the reaction system. 30mg Cu / MSilicalite-1 zeolite, 0.4mmol sodium benzenesulfinate, 0.2mmol iodobenzene, and 1mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130°C heater under air atmosphere for 3h. After cooling to room temperature, the reaction liquid was filtered. The conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of diphenyl sulfide was 93%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically, a mixture of petroleum ether (PE) and ethyl acetate (EA) was used as the eluent (developing agent), and the product was eluted and separated by silica gel column chromatography. The characterization data of the product are as follows: 1 H NMR(400MHz,Chloroform-d)δ7.36-7.20(m,10H).

[0037] Embodiment 2:

[0038] A 10 mL Schlenk reaction tube was used as a container for the reaction system, 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol iodobenzene, and 1 mL tetrahydrofuran were added to the reaction tube, and the reaction was carried out in a 130° C. heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered, and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of diphenyl sulfide was 15%, and the remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically, a mixture of petroleum ether (PE) and ethyl acetate (EA) was used as an eluent (developing agent), and silica gel column chromatography was used for elution and separation to obtain the product.

[0039] If the solvent in Example 2 is replaced with 1 mL of toluene and other conditions remain unchanged, the conversion rate and selectivity are measured by LC, and the yield of diphenyl sulfide is 6%.

[0040] If the solvent in Example 2 is replaced with 1 mL of dichloroethane, and other conditions remain unchanged, the conversion rate and selectivity are measured by LC, and the yield of diphenyl sulfide is 16%.

[0041] If the solvent in Example 2 is replaced with 1 mL of dimethyl sulfoxide, and other conditions remain unchanged, the conversion rate and selectivity are determined by LC, and the yield of diphenyl sulfide is 57%.

[0042] If the solvent in Example 2 is replaced with 1 mL of 1,4-dioxane, and other conditions remain unchanged, the conversion rate and selectivity are determined by LC, and the yield of diphenyl sulfide is 49%.

[0043] Embodiment 3:

[0044] A 10 mL Schlenk reaction tube was used as a container for the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol iodobenzene, and 1 mL N,N-dimethylformamide were added to the reaction tube. The mixture was reacted in a 100 ° C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered. The conversion rate and selectivity of the reaction were analyzed using liquid chromatography (LC). The final calculated yield of diphenyl sulfide was 56%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically, a mixture of petroleum ether (PE) and ethyl acetate (EA) was used as an eluent (developing agent), and silica gel column chromatography was used for elution and separation to obtain the product.

[0045] If the temperature in Example 3 is increased to 120° C. and other conditions remain unchanged, the conversion rate and selectivity are measured by LC, and the yield of diphenyl sulfide is 75%.

[0046] If the temperature in Example 3 is increased to 140° C. and other conditions remain unchanged, the conversion rate and selectivity are measured by LC, and the yield of diphenyl sulfide is 91%.

[0047] Embodiment 4:

[0048] A 10 mL Schlenk reaction tube was used as a container for the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol iodobenzene, and 1 mL N,N-dimethylformamide were added to the reaction tube. The mixture was reacted in a 130° C. heater under air atmosphere for 1 h. After cooling to room temperature, the reaction solution was filtered. The conversion rate and selectivity of the reaction were analyzed using liquid chromatography (LC). The final calculated yield of diphenyl sulfide was 57%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically, a mixture of petroleum ether (PE) and ethyl acetate (EA) was used as an eluent (developing agent), and silica gel column chromatography was used for elution and separation to obtain the product.

[0049] If the reaction time in Example 4 is changed to 2 h, and other conditions remain unchanged, the conversion rate and selectivity are measured by LC, and the yield of diphenyl sulfide is 81%.

[0050] If the time in Example 4 is changed to 4 h, and other conditions remain unchanged, the conversion rate and selectivity are measured by LC, and the yield of diphenyl sulfide is 90%.

[0051] Embodiment 5:

[0052]

[0053] A 10 mL Schlenk reaction tube was used as the container of the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol 4-iodotoluene, and 1 mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130 ° C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of 4-methyldiphenyl sulfide was 90%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically using a mixture of petroleum ether (PE) and ethyl acetate (EA) as the eluent (developing agent), and eluted and separated by silica gel column chromatography to obtain the product. The characterization data of the product are as follows: 1 H NMR (400MHz, Chloroform-d) δ7.34 (ddd, J=52.9, 22.8, 8.0Hz, 8H), 2.45 (s, 3H).

[0054] Embodiment 6:

[0055]

[0056] A 10 mL Schlenk reaction tube was used as the container of the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol p-iodoaniline, and 1 mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130 ° C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of 2-aminodiphenyl sulfide was 83%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically using a mixture of petroleum ether (PE) and ethyl acetate (EA) as the eluent (developing agent), and eluted and separated by silica gel column chromatography to obtain the product. The characterization data of the product are as follows: 1 HNMR(400MHz,Chloroform-d)δ7.18(d,J=8.6Hz,2H),7.10-6.93(m,5H),6.49(d,J=8.5Hz,2H),3.56(s,2H).

[0057] Embodiment 7:

[0058]

[0059] A 10 mL Schlenk reaction tube was used as the container of the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol 2-fluoroiodobenzene, and 1 mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130°C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered. The conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of (2-fluorophenyl)(phenyl)sulfane was 73%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically, a mixture of petroleum ether (PE) and ethyl acetate (EA) was used as the eluent (developing agent), and the product was eluted and separated by silica gel column chromatography. The characterization data of the product are as follows: 1 HNMR(400MHz,Chloroform-d)δ7.29-7.16(m,7H),7.02(q,J=9.6,8.3Hz,2H).

[0060] Embodiment 8:

[0061]

[0062] A 10 mL Schlenk reaction tube was used as the container of the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol p-bromoiodobenzene, and 1 mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130 ° C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of 4-bromodiphenyl sulfide was 75%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically using a mixture of petroleum ether (PE) and ethyl acetate (EA) as the eluent (developing agent), and eluted and separated by silica gel column chromatography to obtain the product. The characterization data of the product are as follows: 1 HNMR (400MHz, Chloroform-d) δ7.33-7.16 (m, 7H), 7.08 (d, J = 8.5Hz, 2H).

[0063] Embodiment 9:

[0064]

[0065] A 10 mL Schlenk reaction tube was used as the container of the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol p-fluoroiodobenzene, and 1 mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130 ° C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of 4-fluorodiphenyl sulfide was 75%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically using a mixture of petroleum ether (PE) and ethyl acetate (EA) as the eluent (developing agent), and eluted and separated by silica gel column chromatography to obtain the product. The characterization data of the product are as follows: 1 HNMR (400MHz, Chloroform-d) δ7.33 (dd, J=8.6, 5.4Hz, 2H), 7.20 (dd, J=26.7, 4.4Hz, 5H), 6.96 (t, J=8.6Hz, 2H).

[0066] Embodiment 10:

[0067]

[0068] A 10 mL Schlenk reaction tube was used as the container of the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol 1,3-dimethyl-5-iodobenzene, and 1 mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130 ° C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of 1,3-dimethyl-5-(phenylthio)benzene was 75%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically using a mixture of petroleum ether (PE) and ethyl acetate (EA) as the eluent (developing agent), and eluted and separated by silica gel column chromatography to obtain the product. The characterization data of the product are as follows:

[0069] 1 HNMR(400MHz,Chloroform-d)δ7.24-7.09(m,5H),6.91(s,2H),6.79(s,1H),2.17(s,6H).

[0070] Embodiment 11:

[0071]

[0072] A 10 mL Schlenk reaction tube was used as the container of the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol 4-iodobiphenyl, and 1 mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130 ° C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of 4-(phenylthio)-1,1'-biphenyl was 80%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically using a mixture of petroleum ether (PE) and ethyl acetate (EA) as the eluent (developing agent), and eluted and separated by silica gel column chromatography to obtain the product. The characterization data of the product are as follows: 1 HNMR (400MHz, Chloroform-d) δ7.43 (dd, J=17.3, 8.1Hz, 4H), 7.34-7.07 (m, 10H).

[0073] Embodiment 12:

[0074]

[0075] A 10 mL Schlenk reaction tube was used as the container of the reaction system. 30 mg Cu / MSilicalite-1 zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol 3,5-dichloroiodobenzene, and 1 mL N,N-dimethylformamide were added to the reaction tube. The reaction was carried out in a 130 ° C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of 1,3-dichloro-5-benzylthiobenzene was 60%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically using a mixture of petroleum ether (PE) and ethyl acetate (EA) as the eluent (developing agent), and eluted and separated by silica gel column chromatography to obtain the product. The characterization data of the product are as follows: 1 HNMR(400MHz,Chloroform-d)δ7.37-7.32(m,2H),7.27(d,J=5.2Hz,3H),7.03(s,1H),6.95(s,2H).

[0076] Comparative Example 1:

[0077] Comparative Example 1 is compared with Example 1, except that MSilicalite is replaced by Beta. The preparation method of Beta is the same as that of CN202410082294.0. The preparation method of Cu / Beta zeolite is the same as that of Cu / MSilicalite-1.

[0078] 30 mg Cu / Beta zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol iodobenzene, and 1 mL N,N-dimethylformamide were added to a reaction tube, and the mixture was reacted in a 130° C. heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered, and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of diphenyl sulfide was 15%, and the remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically, a mixture of petroleum ether (PE) and ethyl acetate (EA) was used as an eluent (developing agent), and silica gel column chromatography was used for elution and separation to obtain the product.

[0079] Comparative Example 2:

[0080] Comparative Example 2 is compared with Example 1, except that MSilicalite is replaced by ETS-10. The preparation method of ETS-10 is the same as CN202211177925.4. The preparation method of Cu / ETS-10 zeolite is the same as Cu / MSilicalite-1.

[0081] 30 mg of Cu / ETS-10 zeolite, 0.4 mmol of sodium benzenesulfinate, 0.2 mmol of iodobenzene, and 1 mL of N,N-dimethylformamide were added to a reaction tube, and the mixture was reacted in a 130°C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC), and it was found that no target product was generated.

[0082] Comparative Example 3:

[0083] 0.009 mmol of copper nitrate, 0.4 mmol of sodium benzenesulfinate, 0.2 mmol of iodobenzene and 1 mL of N,N-dimethylformamide were added to the reaction tube, and the mixture was reacted in a 130°C heater under air atmosphere for 3 h. After cooling to room temperature, the reaction solution was filtered, and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of diphenyl sulfide was 35%. The remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically, a mixture of petroleum ether (PE) and ethyl acetate (EA) was used as an eluent (developing agent), and eluted and separated by silica gel column chromatography to obtain the product.

[0084] Keeping other reaction conditions unchanged, the amount of copper nitrate used in Comparative Example 3 was changed to 30 mg, and the final yield of diphenyl sulfide was calculated to be 58%.

[0085] Comparative Example 4:

[0086] Comparative Example 4 is compared with Example 1, except that Cu / MSilicalite is replaced by MSilicalite. 30 mgMSilicalite zeolite, 0.4 mmol sodium benzenesulfinate, 0.2 mmol iodobenzene, and 1 mL N,N-dimethylformamide were added to the reaction tube, and reacted in a 130°C heater for 3 h under air atmosphere. After cooling to room temperature, the reaction solution was filtered, and the conversion rate and selectivity of the reaction were analyzed by liquid chromatography (LC). The final calculated yield of diphenyl sulfide was 23%, and the remaining organic mixture was separated by column chromatography or thin layer chromatography, specifically, a mixture of petroleum ether (PE) and ethyl acetate (EA) was used as an eluent (developing agent), and silica gel column chromatography was used for elution and separation to obtain the product.

Claims

1. A method for synthesizing an aryl sulfide compound, characterized in that: Aryl sulfinic acid sodium salt and aryl iodide are added as raw materials into a reaction solvent, and Cu / MSilicalite-1 is used as a catalyst to react under heating conditions to obtain an aryl sulfide compound; The reaction structure is as follows: R1 is selected from hydrogen, amino, alkyl, halogen, alkoxy, aryl or substituted aryl.

2. The method for synthesizing aryl sulfide compounds according to claim 1, characterized in that: The reaction solvent is one of dimethyl sulfoxide, N,N-dimethylformamide and 1,4-dioxane.

3. The method for synthesizing aryl sulfide compounds according to claim 1, characterized in that: The molar ratio of the arylsulfinic acid sodium salt to the aryl iodide is 5:1 to 1:

1.

4. The method for synthesizing aryl sulfide compounds according to claim 1, characterized in that: The molar amount of the aryl iodide and the mass ratio of Cu / MSilicalite-1 are 1:100 to 1:200 mol / g.

5. The method for synthesizing aryl sulfide compounds according to claim 1, characterized in that: The copper loading mass in Cu / MSilicalite-1 zeolite is 1% to 10%.

6. The method for synthesizing aryl sulfide compounds according to claim 1, characterized in that: The heating reaction temperature is 100-160°C and the reaction time is 1-5h.

7. The method for synthesizing aryl sulfide compounds according to claim 1, characterized in that: The structure of MSilicalite is a specific surface area of ​​350-450m 2 / g, and the mesopore volume is 0.1~0.20cm 3 / g, with an external surface area of ​​100 to 180 m 2 / g, micropore volume is 0.09~0.16cm 3 / g.

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