A preparation method of diphenyl diselenide

Abstract

The invention discloses a method for preparing diphenyl diselenide, which is characterized by comprising the following steps: reacting phenylselenous acid with two-dimensional nano material titanium carbide Ti3C2T x Mix in water, react at room temperature and pressure to generate nano material TiO2 and diphenyl diselenide adsorbed on the surface of TiO2; collect TiO2 by centrifugation and disperse in an organic solvent, dissolve the diphenyl diselenide in the organic solvent, remove TiO2 by centrifugation, and obtain the diphenyl diselenide. x The reducibility of nanomaterials can reduce phenylselenous acid to diphenyl diselenide, and Ti3C2T x The nanomaterial TiO2 generated after the reaction is insoluble in water, and the hydrophobic adsorption of the nanomaterial surface adsorbs the product diphenyl diselenide, which is also insoluble in water, on the surface of the nanomaterial, and then is quickly separated by taking advantage of the easy separation of solid and liquid. The reaction process is carried out at room temperature and pressure, with mild conditions and no toxic reactants.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical synthesis, and particularly relates to a method for preparing diphenyldiselenide. Background Art

[0002] Selenium is an essential trace element for the human body. In recent years, with the deepening of research on selenides, it has gradually been recognized that compared with inorganic selenides, organic selenides have the following characteristics: 1) richer structures and types; 2) more conducive to cell uptake; 3) more conducive to biotransformation. Among them, diphenyldiselenide is one of the most intensively studied organic selenides, and the reported effects include neuroprotection, antidepressant, anti-inflammatory, cardioprotection, liver protection, anti-cancer, antibacterial, antiviral and other effects, and has great potential for biological applications.

[0003] Currently, the synthesis method of diphenyldiselenide is mainly a liquid-liquid homogeneous reaction, which has the following defects: 1) The liquid-liquid homogeneous reaction occurs in organic reagents, and the separation and purification process of by-products and substrates is complex, with high costs and low efficiency; 2) Most of the reaction conditions involve high-temperature conditions; 3) There are reactants with poor biocompatibility (such as sodium sulfide and bromobenzene) in the reaction process, which affect its biological applications.

[0004] Therefore, it is of great significance to research and develop a preparation method of diphenyldiselenide with simple and non-toxic reactant components, simple, efficient recovery and purification operations, and high reaction efficiency. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the present invention provides a method for preparing solid-liquid heterogeneous diphenyldiselenide, which synthesizes diphenyldiselenide gently at normal temperature and pressure in a pure water system. The reaction is efficient and convenient, without toxic reactants, and at the same time, the rapid recovery is achieved by means of the adsorption of diphenyldiselenide by solid-phase nanomaterials; it solves the problems of toxic reactants, harsh conditions, and cumbersome and inefficient recovery steps of diphenyldiselenide products in the current diphenyldiselenide synthesis methods.

[0006] To solve the above technical problems, the present invention provides a method for preparing diphenyldiselenide, which includes the following steps:

[0007] S1. Mix benzeneseleninic acid with two-dimensional nanomaterial titanium carbide Ti 3 C 2 T x in water and react under normal temperature and pressure conditions to generate nanomaterial titanium dioxide TiO 2 and diphenyldiselenide adsorbed on the surface of the titanium dioxide TiO 2 . The reaction process is as follows:

[0008]

[0009] S2. Centrifuge and collect titanium dioxide TiO adsorbed with diphenyldiselenide 2 , and disperse it in an organic solvent. The diphenyldiselenide is dissolved in the organic solvent, and the insoluble solid nanomaterial titanium dioxide TiO is removed by centrifugation 2 to obtain the diphenyldiselenide.

[0010] In the present invention, an aqueous solution of benzeneseleninic acid is mixed with two-dimensional nanomaterial titanium carbide (Ti 3 C 2 T x ) solid particles, and the reaction can occur under normal temperature and pressure, generating solid titanium dioxide (TiO 2 ) nanoparticles and diphenyldiselenide; the diphenyldiselenide is adsorbed on the surface of the solid nanoparticles and is insoluble in the aqueous solution. At this time, centrifuge and collect the titanium dioxide TiO 2 particles, and redisperse them in an organic solvent. The diphenyldiselenide is dissolved in the organic solvent, and the solid titanium dioxide TiO 2 nanoparticles are removed to obtain the diphenyldiselenide solution. The present invention utilizes the reducibility of the Ti 3 C 2 T x nanomaterial to reduce benzeneseleninic acid to diphenyldiselenide. At the same time, by utilizing the characteristics of the solid-liquid heterogeneous reaction and the water-insolubility of the product diphenyldiselenide and the nanomaterial TiO 2 , the two are combined through hydrophobic interaction, thereby immobilizing the diphenyldiselenide on the surface of the titanium dioxide particles, and then quickly separating it by virtue of the easy separation of solid and liquid; the reaction process is carried out under normal temperature and pressure, with mild conditions and no toxic reactants.

[0011] Further, the size of the two-dimensional nanomaterial Ti 3 C 2 T x is 50 - 850 nm.

[0012] Further, the T 3 C 2 T x in the two-dimensional nanomaterial represents one or more of the functional groups -OH, -F, -Cl, -O possessed by the material. x

[0013] Further, the mass ratio of the benzeneseleninic acid to Ti 3 C 2 T x is 1:1 - 3:1.

[0014] Further, the reaction time is 12 - 16 h.

[0015] Further, the centrifugal collection speed is 8000 - 16000 rpm.

[0016] Further, the organic solvent is selected from one or more of ethyl acetate, chloroform, and dichloromethane.

[0017] Further, the preparation method of the Ti 3 C 2 T x comprises the following steps:

[0018] (1) Mix LiF and HCl and react to generate HF, add Ti 3 AlC 2 , and perform etching treatment;

[0019] (2) Centrifuge the slurry after etching treatment repeatedly and separate the precipitate;

[0020] (3) Add deionized water, perform ultrasonic cleaning, centrifugation, and suction filtration to obtain the Ti 3 C 2 T x .

[0021] Further, in step (1), the temperature of the reaction is 35 - 45 °C, and the time is 15 - 30 min;

[0022] And / or, the temperature of the etching treatment is 40 - 45 °C, the reactor rotation speed is 400 - 600 rpm, and the time is 42 - 54 h.

[0023] Further, in step (2), the repeated centrifugation specifically is: centrifuge 7 - 8 times at a rotation speed of 3000 - 4000 rpm and then perform vacuum suction filtration, and continue to centrifuge the precipitate after suction filtration until viscous precipitate and supernatant appear.

[0024] Further, in step (3), the pore size of the suction filtration membrane is ≤ 0.22 μm.

[0025] Further, after step (3), it also includes the steps of vacuum drying and grinding.

[0026] Further, the temperature of the vacuum drying is 40 °C, and the time is 8 h.

[0027] Advantages of the present invention:

[0028] In the present invention, phenylselenic acid is mixed with two-dimensional nanomaterial titanium carbide Ti 3 C 2 T x and reacted in a pure water system, and Ti 3 C 2 T xThe reducing property of the nanomaterial reduces phenylselenious acid to diphenyldiselenide. Meanwhile, by using Ti 3 C 2 T x The titanium dioxide TiO of the nanomaterial generated after the reaction 2 is insoluble in water. And due to the hydrophobic adsorption property of the nanomaterial surface, the product diphenyldiselenide which is also insoluble in water is adsorbed on the surface of the nanomaterial, and then rapid separation is carried out by virtue of the characteristics of easy solid-liquid separation. This solves the problems of toxic reactants, harsh conditions, and cumbersome and inefficient recovery steps of diphenyldiselenide products in the current diphenyldiselenide synthesis methods.

[0029] The reaction process of the present invention is carried out under normal temperature and pressure, with mild conditions, no other by-products, and no toxic reactants. Brief Description of the Drawings

[0030] In order to more clearly illustrate the technical solutions of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only the embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0031] Figure 1 is the atomic force microscope picture of the two-dimensional nanomaterial titanium carbide Ti 3 C 2 T x prepared in Example 1 of the present invention;

[0032] Figure 2 is the nuclear magnetic resonance characterization of diphenyldiselenide prepared in Example 2 of the present invention;

[0033] Figure 3 is the high performance liquid chromatography characterization of diphenyldiselenide prepared in Example 2 of the present invention;

[0034] Figure 4 is the X-ray diffraction characterization of the nanomaterial before and after the reaction in Example 3 of the present invention;

[0035] Figure 5 is the ICP-OES detection result of selenium element in the experimental group and the control group in Example 4 of the present invention;

[0036] Figure 6 is the X-ray photoelectron spectroscopy characterization of the nanomaterial before and after the reaction in Example 5 of the present invention. Detailed Embodiments

[0037] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0038] The following are specific embodiments

[0039] Example 1

[0040] This example relates to a preparation method of two-dimensional nanomaterial titanium carbide Ti 3 C 2 T x and includes the following steps:

[0041] (1) Add 3.2 g of LiF and 40 mL of 9 M HCl to a polytetrafluoroethylene (100 mL) autoclave and react at 40 °C for 15 min;

[0042] (2) Weigh 2 g of titanium aluminum carbide (Ti 3 AlC 2 ) and add it to the autoclave in small portions slowly (about 10 min). Adjust the rotation speed of the reactor to 500 rpm and react at 40 - 45 °C for 48 h;

[0043] (3) After the reaction is completed, pour the above slurry into two 50 mL centrifuge tubes respectively, and centrifuge repeatedly at 3500 rpm for 7 times until the pH reaches 6, then perform vacuum filtration. The precipitate after vacuum filtration is added back to the 50 mL centrifuge tube and continue to centrifuge until a viscous precipitate appears and the upper layer of liquid turns black, then stop centrifugation and pour out the upper layer of liquid;

[0044] (4) Add 50 mL of deionized water to each of the two centrifuge tubes, pour them into a three-necked round-bottom flask. One opening is for passing inert gas, one opening is for fixing the support (plugging), and the last opening is plugged after passing inert gas. Place the above device in an ultrasonic machine with an ice pack and ultrasonicate for 1 h. After ultrasonication, pour the liquid into a 50 mL centrifuge tube and centrifuge at 3000 rpm for 30 min, and finally obtain a dark green dispersion. The precipitate part is filtered through a water-based filter membrane with a pore size of 0.22 um, dried in a vacuum drying oven at 40 °C for 8 h after drying, taken out and ground into powder to obtain two-dimensional nanomaterial titanium carbide Ti 3 C 2 T x , and perform atomic force microscope characterization on Ti 3 C 2 T x , and the results are as Figure 1 shown. It can be seen that Ti 3 C 2 Tx It is a two-dimensional nanosheet structure.

[0045] Example 2

[0046] This example relates to a preparation method of diphenyl diselenide, which includes the following steps:

[0047] S1. Mix 50 μg of benzeneseleninic acid with 50 μg of titanium carbide Ti 3 C 2 T x prepared in Example 1 into 1 ml of water and react in a round-bottom flask;

[0048] S2. Stir and react the mixture at normal temperature and pressure for 12 h to generate the nanomaterial titanium dioxide TiO 2 and diphenyl diselenide adsorbed on the surface of the titanium dioxide TiO 2 ;

[0049] S3. Centrifuge at 16000 rpm to collect titanium dioxide TiO 2 and disperse it in chloroform. Diphenyl diselenide is dissolved in chloroform. Centrifuge at 16000 rpm to remove titanium dioxide TiO 2 to obtain diphenyl diselenide with a yield of 95%.

[0050] Examine the product purity and whether the product is diphenyl diselenide by nuclear magnetic resonance and high performance liquid chromatography. As Figure 2 and Figure 3 shown, it can be seen that diphenyl diselenide is successfully synthesized by this method.

[0051] Example 3

[0052] S1. Mix 100 μg of benzeneseleninic acid with 50 μg of titanium carbide Ti 3 C 2 T x prepared in Example 1 into 1 ml of water and react in a round-bottom flask;

[0053] S2. Stir and react the mixture at normal temperature and pressure for 12 h to generate the nanomaterial titanium dioxide TiO 2 and diphenyl diselenide adsorbed on the surface of the titanium dioxide TiO 2 ;

[0054] S3. Centrifuge at 16000 rpm to collect titanium dioxide TiO 2 and wash the material with deionized water. After washing, centrifuge at 16000 rpm again to collect, and repeat the washing and centrifugation 5 times;

[0055] S4. Then replace the deionized water in step S3 with chloroform and repeat step S3 to remove diphenyl diselenide dissolved in the organic solvent;

[0056] S4. Collect the materials after chloroform washing and centrifugation for 5 times, and place them in an oven at 37 °C overnight to dry, obtaining titanium dioxide TiO 2 ;

[0057] S5. Conduct X-ray diffraction characterization on the titanium dioxide TiO 2 .

[0058] The two-dimensional nanomaterial Ti 3 C 2 T x before the reaction and the X-ray diffraction characterization of the titanium dioxide TiO 2 after the reaction are as shown in Figure 4 . It can be seen that the synthesis method generates titanium dioxide TiO 2 .

[0059] Example 4

[0060] S1. Mix 150 μg of phenylselenic acid with 50 μg of titanium carbide Ti 3 C 2 T x prepared in Example 1 in 1 ml of water and react in a round-bottom flask. This group is the experimental group. Mix 50 μg of titanium carbide Ti 3 C 2 T x prepared in Example 1 in 1 ml of water and react in a round-bottom flask. This group is the control group;

[0061] S2. Stir and react the two groups at normal temperature and pressure for 12 h. The experimental group generates the nanomaterial titanium dioxide TiO 2 and diphenyldiselenide adsorbed on the surface of the titanium dioxide TiO 2 . The control group does not react;

[0062] S3. Centrifuge at 16000 rpm to collect the materials of the experimental group and the control group and wash the materials with deionized water. After washing, centrifuge at 16000 rpm again to collect, and repeat the washing and centrifugation 5 times to completely remove the reaction substrate phenylselenic acid;

[0063] S4. Collect the materials after washing and centrifugation for 5 times, place them in an oven at 37 °C overnight to dry, and add aqua regia (concentrated hydrochloric acid: concentrated nitric acid = 3:1) to the experimental group and the control group for digestion;

[0064] S5. After digestion, use ICP-OES to detect the selenium element content.

[0065] The ICP-OES results of the experimental group and the control group are as shown in Figure 5 . The content of Se element detected in the experimental group is 83.7 times that of the control group. The selenium content in the control group is the background value. It can be seen that the diphenyldiselenide synthesized by this method is adsorbed on the titanium dioxide TiO 2Above.

[0066] Example 5

[0067] S1. Mix 150 μg of phenylselenic acid with 50 μg of titanium carbide Ti 3 C 2 T x in 1 ml of water and react in a round-bottom flask;

[0068] S2. Stir and react the mixture at room temperature and atmospheric pressure for 12 h to produce the nanomaterial titanium dioxide TiO 2 and diphenyldiselenide adsorbed on the surface of the titanium dioxide TiO 2 ;

[0069] S3. Centrifuge at 16000 rpm to collect titanium dioxide TiO 2 and wash the material with deionized water. After washing, centrifuge again at 16000 rpm to collect, and repeat the washing and centrifugation 5 times;

[0070] S4. Collect the material after washing and centrifuging 5 times and place it in an oven at 37 °C overnight to dry;

[0071] S5. Perform X-ray photoelectron spectroscopy characterization on the titanium dioxide TiO 2 and diphenyldiselenide adsorbed on the titanium dioxide TiO 2 .

[0072] The X-ray photoelectron spectroscopy characterization of the two-dimensional nanomaterial Ti 3 C 2 T x before the reaction and the titanium dioxide TiO 2 after the reaction is as Figure 6 shown. It can be seen that diphenyldiselenide is synthesized and titanium dioxide TiO 2 is generated at the same time, and diphenyldiselenide is adsorbed on the titanium dioxide TiO 2 .

[0073] Comparative Example 1

[0074] The difference between this comparative example and Example 2 is that titanium carbide aluminum (Ti 3 AlC 2 ) is used to replace Ti 3 C 2 T x in Example 2. The specific steps are as follows:

[0075] S1. Mix 100 μg of phenylselenic acid with 100 μg of titanium carbide aluminum (Ti 3 AlC 2 ) in 1 ml of water and react in a round-bottom flask;

[0076] S2. The mixture is stirred and reacted at normal temperature and pressure for 12 h;

[0077] S3. Centrifuge to collect the solid material and disperse it in chloroform, then centrifuge to remove the solid material, and detect it by HPLC. The formation of diphenyldiselenide is not detected, indicating that Ti 3 AlC 2 and phenylselenious acid cannot react to form diphenyldiselenide at normal temperature and pressure.

[0078] The present invention has been described in detail above in combination with specific embodiments and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that without departing from the spirit and scope of the present invention, various equivalent substitutions, modifications or improvements can be made to the technical solutions and their implementation manners of the present invention, and these all fall within the scope of the present invention. The protection scope of the present invention is subject to the appended claims.

Claims

1. A method for preparing diphenyl diselenide, characterized in that: The steps include: S1. Phenylselenous acid and two-dimensional nanomaterial titanium carbide Ti3C2T x Mixed in water, reacted at room temperature and pressure to generate nano material titanium dioxide TiO2 and diphenyl diselenide adsorbed on the surface of the titanium dioxide TiO2, the reaction process is: S2, collecting TiO2 adsorbed with diphenyl diselenide by centrifugation, and dispersing the TiO2 in an organic solvent, wherein the diphenyl diselenide is dissolved in the organic solvent, and removing the insoluble solid nano material titanium dioxide TiO2 by centrifugation to obtain the diphenyl diselenide.

2. The method for preparing diphenyl diselenide as claimed in claim 1, wherein The two-dimensional nanomaterial Ti3C2T x The size is 50-850nm.

3. The method for preparing diphenyl diselenide as claimed in claim 1, characterized in that, The phenylselenous acid and Ti3C2T x The mass ratio is 1:1-3:

1.

4. The method for preparing diphenyl diselenide as claimed in claim 1, characterized in that: The reaction time is 12-16h.

5. The method for preparing diphenyl diselenide as claimed in claim 1, characterized in that, The organic solvent is selected from one or more of ethyl acetate, chloroform and dichloromethane.

6. The method for preparing diphenyl diselenide as claimed in claim 1, characterized in that, The Ti3C2T x The preparation method comprises the following steps: (1) LiF and HCl are mixed and reacted to generate HF, which is then added to Ti3AlC2 for etching; (2) repeatedly centrifuging the etched slurry to separate the precipitate; (3) adding deionized water, ultrasonic cleaning, centrifugation, and suction filtration to obtain the Ti3C2T x .

7. The method for preparing diphenyl diselenide as claimed in claim 6, characterized in that: In step (1), the reaction temperature is 35-45°C and the reaction time is 15-30 min; And / or, the etching treatment temperature is 40-45° C., the reactor speed is 400-600 rpm, and the time is 42-54 h.

8. The method for preparing diphenyl diselenide as claimed in claim 6, characterized in that: In step (2), the repeated centrifugation specifically includes: centrifuging at a speed of 3000-4000 rpm for 7-8 times and then vacuum filtering, and continuing to centrifuge the precipitate after filtration until a viscous precipitate and a supernatant appear.

9. The method for preparing diphenyl diselenide as claimed in claim 6, characterized in that: In step (3), the pore size of the filter membrane used for filtration is ≤0.22 μm.

10. The method for preparing diphenyl diselenide as claimed in claim 6, characterized in that: In step (3), the filtration further includes vacuum drying and grinding steps.

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