Preparation method of diphenyl diselenide

Abstract

The invention discloses a preparation method of diphenyl diselenide, which is characterized by comprising the following steps: mixing benzene seleninic acid and two-dimensional nano material titanium carbide Ti3C2Tx in water, and reacting at normal temperature and normal pressure to generate nano material TiO2 and diphenyl diselenide adsorbed on the surface of TiO2, and centrifuging to collect TiO2, dispersing the TiO2 in an organic solvent, dissolving the diphenyl diselenide in the organic solvent, and centrifuging to remove TiO2 to obtain the diphenyl diselenide. According to the method, benzene seleninic acid is reduced into diphenyl diselenide by utilizing the reducibility of a Ti3C2Tx nano material, meanwhile, the product diphenyl diselenide which is also insoluble in water is adsorbed on the surface of the nano material by utilizing the characteristics that the nano material TiO2 generated after the reaction of Ti3C2Tx is insoluble in water and the surface of the nano material has hydrophobic adsorbability, and then rapid separation is carried out by virtue of the characteristic that solid and liquid are easy to separate; the reaction process is carried out at normal temperature and normal pressure, conditions are mild, and toxic reactants are avoided.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a method for preparing diphenyl diselenide. Background Art

[0002] Selenium is a trace element necessary for the human body. In recent years, as people have studied selenides more and more deeply, they have gradually realized that compared with inorganic selenides, organic selenides have 1) more abundant structures and types; 2) more conducive to cellular uptake; 3) more conducive to biotransformation. Among them, diphenyl diselenide is one of the most intensively studied organic selenides. The effects reported in the research include neuroprotection, anti-depression, anti-inflammation, cardioprotection, liver protection, anti-cancer, antibacterial, antiviral and other effects, and it has great potential for biological applications.

[0003] At present, the synthesis method of diphenyl diselenide is mainly a liquid-liquid homogeneous reaction, which has the following defects: 1) the liquid-liquid homogeneous reaction occurs in an organic reagent, and the by-products and substrates require a complex separation and purification process, which is costly and inefficient; 2) the reaction conditions mostly involve high temperature conditions; 3) the reaction process contains reactants with poor biocompatibility (such as sodium sulfide and bromobenzene), which affects its biological application.

[0004] Therefore, it is of great significance to study and develop a method for preparing diphenyl diselenide with simple and non-toxic reactant components, simple and efficient recovery and purification operations, and high reaction efficiency. Summary of the invention

[0005] The invention aims at the deficiencies in the prior art and provides a method for preparing solid-liquid heterogeneous diphenyl diselenide. In a pure water system, diphenyl diselenide is mildly synthesized at room temperature and pressure, and the reaction is efficient and convenient without toxic reactants. Meanwhile, rapid recovery is achieved by adsorbing diphenyl diselenide with solid-phase nanomaterials. The invention solves the problems of toxic reactants, harsh conditions, and complicated recovery steps and low efficiency of diphenyl diselenide products in the current diphenyl diselenide synthesis method.

[0006] In order to solve the above technical problems, the present invention provides a method for preparing diphenyl diselenide, comprising the following steps:

[0007] 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:

[0008]

[0009] S2, collecting titanium dioxide TiO2 adsorbed with diphenyl diselenide by centrifugation, and dispersing the titanium dioxide 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.

[0010] The present invention combines the phenylselenous acid aqueous solution with the two-dimensional nano material titanium carbide (Ti3C2T x ) solid particles are mixed, and a reaction occurs at room temperature and pressure to generate solid titanium dioxide (TiO2) nanoparticles and diphenyl diselenide; diphenyl diselenide is adsorbed on the surface of the solid nanoparticles and is insoluble in aqueous solution. At this time, the titanium dioxide TiO2 particles are collected by centrifugation and redispersed in an organic solvent, the diphenyl diselenide is dissolved in the organic solvent, the solid titanium dioxide TiO2 nanoparticles are removed, and the diphenyl diselenide solution is obtained. The present invention utilizes Ti3C2T x The reducing property of the nanomaterial can reduce phenylselenous acid to diphenyl diselenide. At the same time, the characteristics of solid-liquid heterogeneous reaction are utilized, and the water insolubility of the product diphenyl diselenide and the nanomaterial TiO2 are utilized. The two are combined through hydrophobic interaction, thereby fixing diphenyl diselenide on the surface of titanium dioxide particles, and then quickly separating it with the help 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.

[0011] Furthermore, the two-dimensional nanomaterial Ti3C2T x The size is 50-850nm.

[0012] Furthermore, the two-dimensional nanomaterial Ti3C2T x T x It indicates one or more of the functional groups -OH, -F, -Cl, and -O possessed by the material.

[0013] Furthermore, the phenylselenous acid and Ti3C2T x The mass ratio is 1:1-3:1.

[0014] Furthermore, the reaction time is 12-16 hours.

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

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

[0017] Furthermore, the Ti3C2T x The preparation method comprises the following steps:

[0018] (1) LiF and HCl are mixed and reacted to generate HF, which is then added to Ti3AlC2 for etching;

[0019] (2) repeatedly centrifuging the etched slurry to separate the precipitate;

[0020] (3) adding deionized water, ultrasonic cleaning, centrifugation, and suction filtration to obtain the Ti3C2T x .

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

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

[0023] Furthermore, in step (2), the repeated centrifugation is specifically: centrifuging at 3000-4000 rpm for 7-8 times and then vacuum filtering, and the precipitate after filtration is further centrifuged until a viscous precipitate and a supernatant appear.

[0024] Furthermore, in step (3), the pore size of the filter membrane used for filtration is ≤0.22 μm.

[0025] Furthermore, in step (3), the filtration further includes the steps of vacuum drying and grinding.

[0026] Furthermore, the vacuum drying temperature is 40° C. and the time is 8 hours.

[0027] Beneficial effects of the present invention:

[0028] The present invention combines phenylselenous acid with two-dimensional nano material titanium carbide Ti3C2T x Mix and react in a pure water system to utilize Ti3C2T x The reducibility of nanomaterials can reduce phenylselenous acid to diphenyl diselenide, and Ti3C2T x The nano material titanium dioxide TiO2 generated after the reaction is insoluble in water, and the hydrophobic adsorption of the surface of the nano material adsorbs the product diphenyl diselenide, which is also insoluble in water, on the surface of the nano material, and then quickly separates it by taking advantage of the easy separation of solid and liquid. This solves the problems of toxic reactants, harsh conditions, and cumbersome and inefficient steps for recovering diphenyl diselenide products in the current diphenyl diselenide synthesis method.

[0029] The reaction process of the invention is carried out at 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 solution of the present invention, the drawings required for use in the embodiments are briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1 The two-dimensional nanomaterial titanium carbide Ti3C2T prepared in Example 1 of the present invention x Atomic force microscope images of

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

[0033] Figure 3 is the HPLC characterization of diphenyl diselenide prepared in Example 2 of the present invention;

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

[0035] Figure 5 The ICP-OES test results of selenium in the experimental group and the control group of Example 4 of the present invention are as follows;

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

[0037] The technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] The following are specific embodiments

[0039] Example 1

[0040] This embodiment relates to a two-dimensional nanomaterial titanium carbide Ti3C2T x The preparation method comprises the following steps:

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

[0042] (2) Weigh 2 g of titanium aluminum carbide (Ti3AlC2) and add it into the kettle in small amounts and slowly (about 10 min), adjust the reactor speed to 500 rpm, and react at 40-45 °C for 48 h;

[0043] (3) After the reaction is completed, the slurry is poured into two 50 mL centrifuge tubes, centrifuged repeatedly at 3500 rpm for 7 times until the pH reaches 6, and then vacuum filtered. The precipitate after vacuum filtration is added back into the 50 mL centrifuge tube and centrifuged continuously until a viscous precipitate appears and the upper liquid turns black, then the centrifugation can be stopped and the upper liquid can be discarded;

[0044] (4) After adding 50 mL of deionized water to each of the two centrifuge tubes, pour them into a three-mouth round-bottom flask, one of which is passed with inert gas, one is used to fix the bracket (blocking), and the last mouth is blocked after the inert gas is passed. The above device is placed in an ultrasonic machine with an ice bag for 1 hour. After the ultrasound is completed, the liquid is poured into a 50 mL centrifuge tube and centrifuged at 3000 rpm for 30 minutes to obtain a dark green dispersion. The precipitated part is filtered through a water filter membrane with a pore size of 0.22 um, and after drying, it is placed in a 40-degree vacuum drying oven for 8 hours. After being taken out, it is ground into powder to obtain a two-dimensional nanomaterial titanium carbide Ti3C2T x , Ti3C2T x Atomic force microscopy was performed and the results were as follows Figure 1 As shown. It can be seen that Ti3C2T x It is a two-dimensional nanosheet structure.

[0045] Example 2

[0046] This embodiment relates to a method for preparing diphenyl diselenide, comprising the following steps:

[0047] S1, 50ug phenylselenous acid and 50ug titanium carbide Ti3C2T prepared in Example 1 x Mix into 1 ml of water and react in a round-bottom flask;

[0048] S2, the mixture is stirred and reacted at room temperature and pressure for 12 hours to generate nano material titanium dioxide TiO2 and diphenyl diselenide adsorbed on the surface of the titanium dioxide TiO2;

[0049] S3. Collect titanium dioxide TiO2 by centrifugation at 16000 rpm and disperse it in chloroform. Dissolve diphenyl diselenide in chloroform. Remove titanium dioxide TiO2 by centrifugation at 16000 rpm to obtain diphenyl diselenide. The yield is 95%.

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

[0051] Example 3

[0052] S1, 100ug phenylselenous acid and 50ug titanium carbide Ti3C2T prepared in Example 1 x Mix into 1 ml of water and react in a round-bottom flask;

[0053] S2, the mixture is stirred and reacted at room temperature and pressure for 12 hours to generate nano material titanium dioxide TiO2 and diphenyl diselenide adsorbed on the surface of the titanium dioxide TiO2;

[0054] S3, centrifuge at 16000 rpm to collect titanium dioxide TiO2 and wash the material with deionized water, centrifuge at 16000 rpm again after washing, and repeat the washing and centrifugation for 5 times;

[0055] S4, replacing the deionized water in step S3 with chloroform, and repeating step S3 to remove the diphenyl diselenide dissolved in the organic solvent;

[0056] S4, collecting the material after chloroform washing and centrifugation for 5 times, and drying it in an oven at 37°C overnight to obtain titanium dioxide TiO2;

[0057] S5. Perform X-ray diffraction characterization on titanium dioxide TiO2.

[0058] Two-dimensional nanomaterial Ti3C2T before reaction x And the X-ray diffraction characterization of titanium dioxide TiO2 after reaction is as follows Figure 4 As shown, it can be seen that the synthesis method produces titanium dioxide TiO2.

[0059] Example 4

[0060] S1, 150ug phenylselenous acid and 50ug titanium carbide Ti3C2T prepared in Example 1 x Mix with 1 ml of water and react in a round-bottom flask. This group is the experimental group. 50 ug of titanium carbide Ti3C2T prepared in Example 1 x Mix with 1 ml of water and react in a round-bottom flask. This group is the control group.

[0061] S2. The two groups were stirred and reacted at room temperature and pressure for 12 hours. The experimental group produced nanomaterial titanium dioxide TiO2 and diphenyl diselenide adsorbed on the surface of the titanium dioxide TiO2, while the control group did not react.

[0062] S3, collect the materials of the experimental group and the control group by centrifugation at 16000 rpm and wash the materials with deionized water, collect them by centrifugation at 16000 rpm again after washing, repeat the washing and centrifugation for 5 times to completely remove the reaction substrate phenylselenous acid;

[0063] S4. Collect the materials after washing and centrifugation for 5 times, place them in a 37°C oven for drying overnight, 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 content.

[0065] The ICP-OES results of the experimental group and the control group are as follows Figure 5 As shown, the Se content detected in the experimental group is 83.7 times that of the control group, wherein the selenium content of the control group is the background value. It can be seen that the diphenyl diselenide synthesized by this method is adsorbed on the titanium dioxide TiO2.

[0066] Example 5

[0067] S1, 150ug phenylselenous acid and 50ug titanium carbide Ti3C2T prepared in Example 1 x Mix into 1 ml of water and react in a round-bottom flask;

[0068] S2, the mixture is stirred and reacted at room temperature and pressure for 12 hours to generate nano material titanium dioxide TiO2 and diphenyl diselenide adsorbed on the surface of the titanium dioxide TiO2;

[0069] S3, centrifuge at 16000 rpm to collect titanium dioxide TiO2 and wash the material with deionized water, centrifuge at 16000 rpm again after washing, and repeat the washing and centrifugation for 5 times;

[0070] S4, collecting the material after washing and centrifugation for 5 times, and drying it in a 37°C oven overnight;

[0071] S5. Perform X-ray photoelectron spectroscopy to characterize titanium dioxide TiO2 and diphenyl diselenide adsorbed on the titanium dioxide TiO2.

[0072] Two-dimensional nanomaterial Ti3C2T before reaction x And the X-ray photoelectron spectroscopy characterization of titanium dioxide TiO2 after reaction is as follows Figure 6 As shown, it can be seen that the method synthesizes diphenyl diselenide and generates titanium dioxide TiO2 at the same time, and the diphenyl diselenide is adsorbed on the titanium dioxide TiO2.

[0073] Comparative Example 1

[0074] The difference between this comparative example and Example 2 is that titanium aluminum carbide (Ti3AlC2) is used to replace the Ti3C2T2 in Example 2. x , the specific steps are:

[0075] S1. Mix 100ug of phenylselenous acid and 100ug of titanium aluminum carbide (Ti3AlC2) into 1ml of water and react in a round-bottom flask;

[0076] S2, the mixture was stirred and reacted at room temperature and pressure for 12 hours;

[0077] S3. The solid material was collected by centrifugation and dispersed in chloroform. The solid material was removed by centrifugation again. HPLC was used for detection. No diphenyl diselenide was detected, indicating that Ti3AlC2 and phenylselenous acid could not react to form diphenyl diselenide at room temperature and pressure.

[0078] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached 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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