Carbohydrate silicon etherified derivative as well as synthesis method and application thereof

Abstract

The invention relates to the technical field of high polymer materials and application thereof, and particularly discloses a carbohydrate silicon etherified derivative. The carbohydrate silicon etherified derivatives provided by the invention have a physical insecticidal effect, and when the derivatives are used as physical insecticides to carry out insecticidal activity tests on citrus red mites, the results show that the carbohydrate silicon etherified derivatives have a good physical killing effect on the citrus red mites; wherein the insecticidal fatality rate LC50 of sucrose tert-butyl dimethyl silyl ether to red spiders is 28.14 + / -0.54 mg / L, which is much better than that of positive control mineral oil; the composition is used for preventing and treating mite pests, has a good killing effect, is harmless to the environment, is environment-friendly, and does not have pest resistance to drugs.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials and their application, and in particular to a saccharide silicon ether derivative and a synthesis method and application thereof. Background Art

[0002] At present, the overall dosage of chemical pesticides used to control mites has reached an extremely high level, but due to the resistance of pests, it is still difficult to obtain satisfactory control effects. The result is the abuse of chemical miticides, which pollutes the environment and ecology. Therefore, how to reduce the dosage of pesticides, ensure the safety of agricultural products, or research and develop new low-toxic or non-toxic miticides to protect the environment and ecology has become a major issue of concern to the whole society. In the past decade, due to the rapid development of materials science and chemistry, many new environmentally friendly materials, new technologies and new compounds have emerged, providing new development opportunities for the research and development of physical action mechanism pesticides. For example, studies on some emerging pesticides have shown that they can kill pests through a physical mechanism of action that dissolves the wax layer on the surface of insects, causing the insects to dehydrate and die (Appah S, Jia WD, Wang MX, et al. Eric Amoah. Analysis of potential impaction and phytotoxicity of surfactant-plant surface interaction in pesticide application [J]. Crop Protection, 2020, 127: 104961.; Glória CMD, Anderson OS, Attilio CM, et al. Biosurfactants: Promising Biomolecules for Agricultural Applications [J]. Sustainability, 2024, 16 (1): 449-481.).

[0003] Silyl ethers are a class of compounds containing a silicon atom and an alkoxy group covalently bonded, with the general formula R1R2R3Si-O-R4. They have been used in carbohydrate chemistry for half a century, but mainly as protective groups for sugar alcohols, carbon-hydrogen activation, carbohydrate activation, etc. (M Bols, TG Frihed, MJ Pedersen, CM Pedersen, Silylated Sugars-Synthesis and Properties, Synlett 2022, 33, 415-428.; M.Mar Kayser, JoséL.de Paz, Pedro M.Nieto, Polymer-Supported Synthesis of Oligosaccharides Using aDiisopropylsiloxane Linker and Trichloroacetimidate Donors, Eur.J.Org.Chem.2010, 2138-2147) There have been many literature reports on the synthesis of oligosaccharide silyl ethers (Anke Flemming, Constantin Mamat, Martin Clemens Krempner, Ralf Miethchen, Novel Carbohydrate-Based Mono-and Bidentate Oligosilyl Ethers, Synthesis 2006, No.16, 2685–2692)[28-29]. In addition, some oligosaccharide silyl ether compounds are also very good surfactants (Fu Han, Yun-yun Deng, Ya-wen Zhou·Bao-cai Xu, Carbohydrate-Modified Silicone Surfactants, J Surfact Deterg, 2012, 15: 123–129).

[0004] Sugar substances are abundant in nature, easy to obtain, and have good biosafety and environmental degradability. Glucose is the most common monosaccharide, and sucrose and lactose are common disaccharides, which are widely available and inexpensive. Silicon is the second most abundant element on Earth, and silicon products have the advantages of being green and pollution-free. The inventors of this application found in their research that by using tert-butyldimethylchlorosilane (TBDMSCl) as a silicon etherification reagent, tert-butyldimethylsilyl groups were introduced into the primary hydroxyl groups of glucose, sucrose and lactose, respectively, and oligosaccharide silyl ether compounds of different structures were synthesized. These oligosaccharide silyl ether compounds have biological activity in killing citrus red spiders, and the lethal effect on red spiders is better than the positive control mineral oil. They can be used as new physical insecticides, which are of great significance for reducing the amount of pesticides, ensuring the safety of agricultural products, and protecting the environment. Summary of the invention

[0005] In view of the above shortcomings, the present invention provides a saccharide silicon ether derivative, which has a good physical killing effect on mite pests. The specific technical scheme is as follows:

[0006] A saccharide silicyl ether derivative, wherein the saccharide silicyl ether derivative has any of the following structural formulas:

[0007]

[0008] On the other hand, the present invention also provides a method for synthesizing the above-mentioned saccharide silane derivative, comprising the following steps:

[0009] The sugar compound is dissolved in a solvent, and then tert-butyldimethylsilyl chloride (TBDMSCl) and an acid binding agent are added, and the reaction is carried out at 0-25°C for 10-90 minutes; after the reaction is completed, the crude product is extracted, dried, and the solvent is removed to obtain a crude product; the crude product is purified and dried by a silica gel column to obtain a sugar silicon ether derivative.

[0010] Preferably, in the above-mentioned method for synthesizing the silylated carbohydrate derivative, the carbohydrate compound is α-methyl glucoside, sucrose, lactose, gentiobiose, melibiose or trehalose.

[0011] Preferably, in the above-mentioned method for synthesizing silylated sugar derivatives, the acid-binding agent is triethylamine or imidazole.

[0012] Preferably, in the above-mentioned method for synthesizing the saccharide silyl ether derivative, the molar ratio of the saccharide compound, tert-butyldimethylchlorosilane and the acid binding agent is 1:1.2-3.5:1.5-5.5.

[0013] Preferably, in the above-mentioned method for synthesizing silylated carbohydrate derivatives, the solvent is any one or more of acetonitrile (MeCN) and N,N-dimethylformamide (DMF).

[0014] On the other hand, the present invention also provides the use of the above-mentioned saccharide silicon ether derivatives in preventing and controlling mite pests.

[0015] Preferably, in the above application, the mite pest is citrus red spider.

[0016] On the other hand, the present invention also provides the use of the above-mentioned saccharide silicon ether derivatives in the preparation of pesticides.

[0017] In another aspect, the present invention further provides an insecticide, which comprises the above-mentioned saccharide silicon ether derivative.

[0018] Preferably, in the above-mentioned pesticide, the saccharide siliconized ether derivative is:

[0019]

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. The saccharide silicyl derivatives of the present invention have physical insecticidal effects. The insecticidal activity of citrus red spider mites was tested by using these derivatives as physical insecticides. The results showed that these saccharide silicyl derivatives had a good physical killing effect on citrus red spider mites, among which the insecticidal lethality LC50 of sucrose tert-butyl dimethyl silyl ether on red spider mites was 28.14±0.54 mg / L, which was much better than the positive control mineral oil. In addition, the biological mechanism of insect death was analyzed by metallographic microscope, electron scanning microscope and laser confocal microscope. The results showed that its lethal biological mechanism was mainly through the dual physical action mode of dissolving the epidermal wax layer of the insect body to cause insect dehydration and blocking the insect trachea to cause suffocation and death.

[0022] 2. The saccharide siliconized ether derivative of the present invention is a physical mechanism insecticide used for controlling mite pests, has good killing effect, is harmless to the environment, is environmentally friendly, and has no pest resistance.

[0023] 3. The synthesis method of the saccharide silane ether derivatives of the present invention is simple, the reaction conditions are mild, the yield is high, and it is conducive to industrial production and its popularization and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are some embodiments of the present invention, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0025] Figure 1The following are the appearance morphologies of different silane-based sugar derivatives sprayed on deadly red spider mites in Application Example 1 of the present invention under a metallographic microscope: (a) a-methyl glucose tert-butyl dimethylsilyl ether; (b) sucrose tert-butyl dimethylsilyl ether; (c) lactose tert-butyl dimethylsilyl ether; (d) water; (e) mineral oil.

[0026] Figure 2 The appearance morphology of the deadly red spider mites sprayed with different saccharide silane derivatives in Application Example 1 of the present invention under an electron microscope: (a) a-methyl glucose tert-butyl dimethyl silane; (b) sucrose tert-butyl dimethyl silane; (c) lactose tert-butyl dimethyl silane; (d) water; (e) mineral oil;

[0027] Figure 3 The appearance of dead red spider mites in 0.1% aniline blue solution of different concentrations of sugar molecule silane in Application Example 2 of the present invention under a laser confocal microscope: (1-1) 50 ppm concentration of α-methyl glucose tert-butyl dimethyl silane; (1-2) 100 ppm concentration of α-methyl glucose tert-butyl dimethyl silane; (1-3) 200 ppm concentration of α-methyl glucose tert-butyl dimethyl silane; (2-1) 50 ppm concentration of sucrose tert-Butyl dimethyl silyl ether; (2-2) 100 ppm concentration of sucrose tert-butyl dimethyl silyl ether; (2-3) 200 ppm concentration of sucrose tert-butyl dimethyl silyl ether; (3-1) 50 ppm concentration of lactose tert-butyl dimethyl silyl ether; (3-2) 100 ppm concentration of lactose tert-butyl dimethyl silyl ether; (3-3) 200 ppm concentration of lactose tert-butyl dimethyl silyl ether; (4) 0.1% aqueous solution of aniline blue dye; (5) water. DETAILED DESCRIPTION

[0028] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments. Unless otherwise defined, all professional terms used hereinafter have the same meaning as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present invention. Unless otherwise specifically stated, various raw materials, reagents, instruments and equipment used in the present invention, etc. can be purchased from the market or can be prepared by existing methods.

[0029] Example 1

[0030] An α-methylglucoside tert-butyl dimethylsilyl ether, the structural formula of which is:

[0031]

[0032] The synthetic route of α-methylglucoside tert-butyl dimethylsilyl ether of the present embodiment is as follows:

[0033]

[0034] The specific synthesis method comprises the following steps:

[0035] Accurately weigh dry α-methyl glucoside (0.388g, 2mmol) in an eggplant-shaped bottle, add 12.5mL dry MeCN and 1.25mL dry DMF solvent, stir at room temperature to completely dissolve. Then add TBDMSCl (0.45g, 3mmol), stir at room temperature for 10min, add triethylamine (0.506mL, 3.6mmol), react for 10min, and use TLC to detect until the reaction is complete. Add appropriate amount of water to stop the reaction, extract with ethyl acetate 3 times, combine the organic phases, dry over anhydrous sodium sulfate, and remove the solvent under reduced pressure to obtain a crude product. Using ethyl acetate as the solvent, a colorless viscous oily crude product of α-methyl glucoside tert-butyl dimethyl silyl ether is obtained after purification by silica gel column chromatography. After further removal of the solvent and drying at room temperature under reduced pressure, 0.401g of α-methyl glucoside tert-butyl dimethyl silyl ether is obtained, with a yield of 64.9%.

[0036] Example 2

[0037] A sucrose tert-butyl dimethyl silyl ether, the structural formula of which is:

[0038]

[0039] The synthetic route of sucrose tert-butyl dimethyl silyl ether of the present embodiment is as follows:

[0040]

[0041] The specific synthesis method comprises the following steps:

[0042] Accurately weigh dry sucrose (0.34g, 1mmol) in an eggplant-shaped bottle, add 15mL of dry DMF solvent, and stir at room temperature for 15min to fully dissolve it. Place the eggplant-shaped bottle in an ice bath, add imidazole (0.36g, 5.3mmol) at 0℃, and continue stirring for 20min until the system is evenly dissolved. Then add TBDMSCl (0.45g, 3mmol), stir and react for 1h, then remove the ice bath, and stir and react at room temperature for 15min. Use TLC to detect until the reaction is complete, add water to terminate the reaction, extract with ethyl acetate 3 times, combine the organic phases, dry over anhydrous sodium sulfate, and remove the solvent under reduced pressure to obtain a crude product. Then use methanol: dichloromethane (1:20) as the solvent, purify it on a silica gel column, and further dry it under reduced pressure to obtain 0.41g of colorless viscous oily sucrose tert-butyl dimethylsilyl ether, with a yield of 59.9%.

[0043] Example 3

[0044] A lactose tert-butyl dimethyl silyl ether, the structural formula of which is:

[0045]

[0046] The synthetic route of lactose tert-butyl dimethyl silyl ether of the present embodiment is as follows:

[0047]

[0048] The synthesis method is similar to that of sucrose tert-butyl dimethyl silyl ether, except that lactose is used instead of sucrose. After purification by silica gel column chromatography, 0.39 g of colorless viscous oily lactose tert-butyl dimethyl silyl ether product is obtained with a yield of 68.4%.

[0049] Application Example 1 Evaluation of the acaricidal activity of saccharide silane derivatives

[0050] Accurately weigh a certain amount of saccharide silane derivatives, dissolve and dilute with distilled water to prepare the test solution with a concentration gradient of 400, 200, 100, 75, 50, and 25 ppm, disperse it evenly with ultrasonic waves, and store the sample solution in a medicine bottle for testing. Inoculate citrus red spider mites (adult mites) (20-25 heads) on fresh peanut leaves, then spray the leaf surface with the test solution evenly, gently place the peanut leaves sprayed with the solution in the experimental box, and investigate the survival rate of the red spider mites after 4 hours. Use commercially available mineral oil as a positive control, and distilled water treatment as a blank control. Evaluate the killing activity of three sugar silane ethers against red spider mites.

[0051] The results are shown in Table 1. From the data in the table, it can be seen that the insecticidal activities of the synthesized α-methyl glucose, sucrose and lactose tert-butyl dimethyl silyl ethers against red spider mites are better than those of commercially available mineral oils. The linear probability analysis fitting results show that sucrose tert-butyl dimethyl silyl ether has the best acaricidal activity among the three, with an IC50 value of 28.14ppm. Its physical insecticidal efficacy is much better than that of mineral oil, and is also better than that of lactose and α-methyl glucose tert-butyl dimethyl silyl ether.

[0052] Table 1 Insecticidal lethality of sugar silyl ether products to red spider mites (unit: ppm)

[0053]

[0054]

[0055] Metallographic microscope analysis

[0056] Take the dead red spider mite body after being treated with saccharide silane derivatives, use a No. 0 brush to lightly pick it up and place it on a glass slide, and place it on the sample stage for observation. Turn on the metallographic microscope and adjust the light source to evenly illuminate the sample stage. Place the prepared red spider mite slide on the sample stage and fix it with a clamp. First use a low-power objective to observe the sample and adjust the focus so that the sample is clearly visible. Then gradually switch to a high-power objective to observe the microscopic structure of the red spider body. Take microscopic photos of the red spider, record the observation results, and analyze the microstructural characteristics of the red spider based on the observation results. Deionized water solution is used as a blank control, and mineral oil is used as a positive control.

[0057] The insecticidal effects of three saccharide silane derivatives on red spider mites were observed under a metallographic microscope. Figure 1 Compared with the red spider pictures of the control group after water treatment, the sugar silicyl ether derivative group had a significant effect on the red spider epidermis, and some areas turned black, indicating that the stratum corneum of its epidermis was partially dissolved and eroded. However, there was no significant difference between the control group using mineral oil and the water control group, which showed that the dissolution of the epidermal lipid layer of the insect body was not the main cause of death caused by mineral oil, but the three sugar silicyl ether derivatives had a certain dissolution effect on the outer lipid layer of the insect body, causing obvious changes in the epidermis.

[0058] Morphological evaluation of dead spider mites - scanning electron microscope analysis

[0059] The dead red spider mites treated with the saccharide silane derivatives were placed in a vacuum freeze dryer at -48°C for freeze drying for 6 hours and then waited for observation. The red spider mites were fixed on the sample stage of the electron scanning microscope using double-sided tape to ensure that the surface of the insect body was clean and free of dust or contaminants. After gold spraying, the sample stage was placed in the sample chamber. Use a low-power microscope to preliminarily locate the observation area, and gradually adjust the magnification until the red spider mites are clearly visible. Adjust the focal length and working distance to obtain the best image clarity, and use SEM to photograph the shape of the red spider mites. Deionized water solution was used as a blank control, and mineral oil was used as a positive control.

[0060] The appearance of the red spider mites that died after spraying the saccharide silane derivatives was observed under an electron scanning microscope after freeze drying in a vacuum freeze dryer at -48°C. Figure 2As shown (distilled water treatment was used as a blank control, and commercially available mineral oil was used as a positive control). As can be seen from the figure, under the observation of an electron scanning microscope, the red spider body obtained after water treatment showed that its appearance was complete and full, without showing any changes. Although the epidermis of the red spider treated with mineral oil was a little sunken, it still maintained a relatively intact appearance. As for the red spider body treated with saccharide silicylates, they all showed significant water loss and shrinkage under an electron scanning microscope. Combined with metallographic microscope observation and analysis, it is speculated that the spraying of saccharide silicylates caused the dissolution of the lipid layer of the insect body's epidermis, resulting in a difference in osmotic pressure inside and outside the insect body, and water loss in the body, which led to the shrinkage and dehydration of the insect body and death.

[0061] Application Example 2: Confocal Laser Microscopy Analysis

[0062] The samples of saccharide silane derivatives were prepared into 200, 100, and 50 ppm test solutions containing 0.1% aniline blue dye. After the red spiders were treated with the solution for 4 hours, the dead red spiders were slowly rinsed with distilled water for 5 minutes to remove the aniline blue dye on the surface. After drying, the red spiders were gently placed on the bottom of a 15 mm laser confocal culture dish with a No. 0 brush, placed on the stage of the laser confocal microscope imaging system, observed and photographed. Distilled water and 0.1% aniline blue dye aqueous solution were used as blank controls, and mineral oil was used as a positive control.

[0063] The laser emission light wave parameters are set as follows: the excitation violet light wavelength is 405nm, and the emission light wavelength is 410-450nm; the excitation blue light wavelength is 488nm, and the emission light wavelength is 490-520nm.

[0064] Figure 3 The following are the appearance morphology of red spiders treated with distilled water, 0.1% aniline blue dye and different concentrations of saccharide silicyl derivative solutions under a laser confocal microscope. It can be observed that the insects treated with water and 0.1% aniline blue dye aqueous solution did not show fluorescence under a laser confocal microscope, indicating that there was no penetration of the solution in their bodies. Red spiders killed by either the positive control mineral oil or saccharide silicyl derivatives showed obvious fluorescence in their mouthparts and abdominal respiratory pores, indicating that these acaricide solutions have penetrated into the insect body and remained in the insect mouthparts and abdominal respiratory pores, causing blockage of the pores, thereby affecting the insect's breathing and causing the insect's death. This confirms that the blockage of insect pores is another biological mechanism of action of sugar silicyl ethers that causes the death of red spiders.

[0065] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. A saccharide silicon ether derivative, characterized in that: The saccharide silicon ether derivative has any of the following structural formulas:

2. A method for synthesizing the saccharide silane ether derivative according to claim 1, characterized in that: The following steps are involved: The sugar compound is dissolved in a solvent, and then tert-butyldimethylsilyl chloride and an acid binding agent are added, and the reaction is carried out at 0-25° C. for 10-90 minutes. After the reaction is completed, the crude product is extracted, dried, and the solvent is removed to obtain a crude product. The crude product is purified and dried by a silica gel column to obtain a sugar silicon ether derivative.

3. The method for synthesizing the saccharide silane ether derivative according to claim 2, characterized in that: The sugar compound is α-methyl glucoside, sucrose, lactose, gentiobiose, melibiose or trehalose.

4. The method for synthesizing the saccharide silane ether derivative according to claim 2, characterized in that: The acid binding agent is triethylamine or imidazole.

5. The method for synthesizing the saccharide silane ether derivative according to claim 2, characterized in that: The molar ratio of the sugar compound, tert-butyldimethylchlorosilane and the acid-binding agent is 1:1.2-3.5:1.5-5.

5.

6. Use of the saccharide silane derivative according to claim 1 in controlling acarid pests.

7. The use according to claim 6, characterized in that: The mite pest is citrus red spider.

8. Use of the saccharide silane derivative according to claim 1 in the preparation of pesticides.

9. An insecticide, characterized in that: The pesticide comprises the saccharide silicon ether derivative according to claim 1.

10. The insecticide according to claim 9, characterized in that The saccharide silicon ether derivative is:

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