A compound containing a semicarbazide (thio)urea structure and its preparation method and application

Abstract

A compound containing a semicarbazide (thio)urea structure has a structural formula as shown in Formula I. The preparation method comprises the following steps of adding aldehyde-containing plant essential oil to a mixture containing thiosemicarbazide, semicarbazide, a phase transfer catalyst and deionized water, performing a sufficient reaction under stirring at room temperature and then subjecting the mixture to post-treatment and purification to obtain the compound containing a semicarbazide (thio)urea structure. The compound has high biological activity against soil-borne pathogenic bacteria, fungi and nematodes, can be widely used in the prevention and treatment of soil-borne diseases, and provides material guarantee for safe production of crops.

Description

Technical Field

[0001] The invention belongs to the technical field of agricultural chemicals, and in particular relates to a compound containing a semicarbazide (thio)urea structure and a preparation method and application thereof. Background Art

[0002] Soilborne diseases are caused by pathogens (bacteria, fungi, nematodes and protozoa, etc.) that live most of their lives in the soil and infect the roots and stems of plants under suitable conditions. Due to the intensive planting and single continuous cropping production models of modern agriculture, pathogens in the soil accumulate year by year, and soilborne diseases have become an important factor restricting the sustainable development of agriculture. The most economical and effective way to prevent and control soilborne diseases is to use chemical agents for prevention and control. However, traditional agents for preventing and controlling soilborne diseases, such as chloropicrin, calcium cyanamide, dazomethane, sulfuryl fluoride, 1,3-dichloropropylene, dimethyl disulfide, pyramidal and methyl bromide, are highly toxic to non-target organisms, easily cause damage to the environment, and the repeated use of a single agent causes increasingly serious resistance. Therefore, the development of efficient, safe and novel compounds to prevent and control soilborne diseases has become an urgent need for sustainable agricultural production.

[0003] Plant essential oils are an important class of botanical pesticides and are secondary metabolites of aromatic plants. Plant essential oils were originally mainly used for the preparation of spices, perfumes, and preservatives. With the continuous deepening of research, various biological activities such as antioxidant, antibacterial, and insect repellent of plant essential oils have been discovered, and have thus attracted widespread attention. In plant essential oils, many aldehyde components, including aromatic aldehydes (such as cinnamaldehyde and p-anisaldehyde) and fatty aldehydes (such as citronellal, citral, and perilla aldehyde) are present in essential oils extracted from various aromatic plants, and are used in the prevention and treatment of plant diseases due to their activity against various pathogens. Although aldehyde-containing plant essential oils have the advantages of high biological activity and good compatibility with biological environments, they are volatile, easily oxidized, poorly water-soluble, inconvenient to store and transport, and have a pungent odor, which affects their practical application in production. Therefore, developing a safe and efficient method to overcome the problems of aldehyde-containing plant essential oils is of great significance for their large-scale production and application.

[0004] Semicarbazide (thio) urea is a commonly used pesticide and pharmaceutical chemical intermediate, which can react with aldehyde-containing and ketone-containing compounds to obtain compounds containing condensed semicarbazide (thio) urea structures. In the reported reaction of aldehyde-containing and ketone-containing compounds with semicarbazide (semicarbazide), the aldehyde-containing compound and semicarbazide (semicarbazide) are added to ethanol, acetic acid is used as a catalyst, and the reaction is stirred at room temperature or under heating conditions, and then recrystallized after sedimentation and filtration to obtain the product. For example, patents EP4112776 and FR2887879 both report that aldehyde and semicarbazide are added in equal moles to a round-bottomed flask, dissolved in ethanol, and a small amount of glacial acetic acid is added to the mixture, and the reaction mixture is heated to reflux for 2-3 hours. The completion of the reaction is monitored by thin layer chromatography. After the reaction is completed, the reaction mixture is cooled to room temperature, and the precipitate is dried after precipitation and filtration to obtain a precipitate, which is then recrystallized and dried from ethanol to obtain the product. Since the solubility of semicarbazide and semicarbazide in organic solvents is low, a large amount of organic solvents are used in this method, which causes a waste of resources and has potential safety hazards to the environment and human body. Summary of the invention

[0005] In order to overcome the deficiencies of the prior art, the present invention provides a compound containing a semicarbazide (thio) urea structure and a preparation method thereof. The present invention prepares a series of compounds containing a semicarbazide (thio) urea structure by addition condensation of an aldehyde-containing plant essential oil compound and a semicarbazide (thio) urea. This type of compound can not only effectively improve the problems existing in the use of aldehyde-containing plant essential oils, but also has high biological activity against soil-borne pathogenic bacteria, fungi, and nematodes, and can be widely used in the prevention and treatment of soil-borne diseases, providing material guarantee for the safe production of crops.

[0006] Specifically, the molecular structure of a compound containing a semicarbazide (thio)urea structure provided by the present invention is shown in Formula I,

[0007]

[0008] Among them, R 1 For S, O;

[0009] Wherein, R is a substituent selected from the following:

[0010]

[0011] The present invention also provides a method for preparing the above-mentioned compound containing a semicarbazide (thio)urea structure, comprising the following steps:

[0012] The first step is to add a certain amount of thiosemicarbazide (semicarbazide), a quaternary ammonium salt phase transfer catalyst, and deionized water into a reaction container and stir and dissolve them at room temperature;

[0013] The second step is to add aldehyde-containing plant essential oil to the reaction solution in the first step, and stir the mixture at room temperature for reaction;

[0014] The third step is to track the reaction progress by thin layer chromatography, and to post-treat the reaction product at the end of the reaction to purify it to obtain a compound containing a semicarbazide (thio)urea structure.

[0015] Wherein, the quaternary ammonium salt phase transfer catalyst in the first step is one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and the amount thereof is: The solvent is deionized water.

[0016] Among them, the aldehyde-containing plant essential oil in the second step is one of cinnamaldehyde, salicylaldehyde, furfural, citral, citronellal, perillaldehyde, trans-dihexenal, vanillin, anisaldehyde, benzaldehyde, phenylpropionaldehyde, hemi-gossypol, magnolia aldehyde, tofu fruit glycoside and sinapinic aldehyde; the molar ratio of the aldehyde-containing plant essential oil to thiosemicarbazide or semicarbazide is 1.0:1.0-1.5; and the reaction time is preferably 0.5-12.0h.

[0017] The semicarbazide (thio)urea structure-containing compound obtained by the invention can be used in preventing and controlling soil-borne Botrytis cinera Pers, Sclerotinia sclerotiorum, Fusarium graminearum, Ralstonia solanacearum and southern root-knot nematode (Meloidogyne incognita).

[0018] The beneficial effects of the present invention are:

[0019] 1) The preparation method uses water as the reaction medium, does not use organic solvents, has low cost, and the preparation process is safe and green;

[0020] 2) The obtained semicarbazide (thio)urea compounds have high biological activity against soil-borne pathogenic fungi, bacteria and nematodes, and can be widely used in the prevention and treatment of soil-borne diseases, providing material guarantee for the safe production of crops. DETAILED DESCRIPTION

[0021] The following uses specific embodiments to describe the implementation methods of the present invention in detail, so that the implementation process of how the present invention applies technical means to solve technical problems and achieve technical effects can be fully understood and implemented accordingly.

[0022] In the following examples, the chemical reagents used are commercial industrial-grade products, and the equipment used is well known in the art.

[0023] Example 1

[0024] 0.91 g (10.0 mmol) of thiosemicarbazide, 0.016 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.32 g (10.0 mmol) of cinnamaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 5 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was fully washed three times with deionized water, filtered and dried to obtain the product with a yield of 90.74%. The structural formula of the product is (I-1).

[0025]

[0026] Example 2

[0027] 0.91g (10.0mmol) thiosemicarbazide, 0.013g tetrabutylammonium chloride and 30mL deionized water were added to a 100mL three-necked flask and stirred to dissolve. Then 1.2g (10.0mmol) salicylaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 6h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 81.19%. The structural formula of the product is (I-2).

[0028]

[0029] Example 3

[0030] 1.37 g (15.0 mmol) of thiosemicarbazide, 0.014 g of benzyltriethylammonium chloride and 45 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 0.96 g (10.0 mmol) of furfural was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 2 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 84.35%. The structural formula of the product is (I-3).

[0031]

[0032] Example 4

[0033] 1.37 g (15.0 mmol) of thiosemicarbazide, 0.010 g of benzyltriethylammonium chloride and 45 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.52 g (10.0 mmol) of citral was added to the system and continued to stir at room temperature (25 ° C). The reaction progress was tracked by thin layer chromatography. After 3 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 87.36%. The structural formula of the product is (I-4).

[0034]

[0035] Example 5

[0036] Add 1.37g (15.0mmol) of thiosemicarbazide, 0.005g of trioctylmethylammonium chloride and 45mL of deionized water to a 100mL three-necked flask and stir to dissolve, then add 1.54g (10.0mmol) of citronellal to the system, continue stirring at room temperature (25°C), and track the reaction progress by thin layer chromatography. After 4h of reaction, remove water and volatile aldehydes by rotary evaporation, wash the solid product three times with deionized water, filter and dry to obtain the product, with a yield of 88.31%. The structural formula of the mL product is (I-5).

[0037]

[0038] Example 6

[0039] 0.91g (10.0mmol) thiosemicarbazide, 0.01g dodecyltrimethylammonium chloride and 30mL deionized water were added to a 100mL three-necked flask and stirred to dissolve, then 1.5g (10.0mmol) perillaldehyde was added to the system, and stirring was continued at room temperature (25°C), and the reaction progress was tracked by thin layer chromatography. After 8h of reaction, water and volatile aldehydes were removed by rotary evaporation, and the solid product was washed three times with deionized water, filtered and dried to obtain the product, with a yield of 89.14%. The structural formula of the product is (I-6).

[0040]

[0041] Example 7

[0042] 0.91g (10.0mmol) thiosemicarbazide, 0.01g tetradecyltrimethylammonium chloride and 30mL deionized water were added to a 100mL three-necked flask and stirred to dissolve, then 0.98g (10.0mmol) trans-dihexenal was added to the system, and stirring was continued at room temperature (25°C), and the reaction progress was tracked by thin layer chromatography. After 5h of reaction, water and volatile aldehydes were removed by rotary evaporation, and the solid product was washed three times with deionized water, filtered and dried to obtain the product, with a yield of 78.24%. The structural formula of the product is (I-7).

[0043]

[0044] Example 8

[0045] 0.91g (10.0mmol) of thiosemicarbazide, 0.01g of tetrabutylammonium bromide and 30mL of deionized water were added to a 100mL three-necked flask and stirred to dissolve. Then 1.52g (10.0mmol) of vanillin was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 0.5h of reaction, water was removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 89.81%. The structural formula of the product is (I-8).

[0046]

[0047] Example 9

[0048] 0.91 g (10.0 mmol) of thiosemicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.36 g (10.0 mmol) of anisaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 10 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 91.75%. The structural formula of the product is (I-9).

[0049]

[0050] Example 10

[0051] 0.91 g (10.0 mmol) of thiosemicarbazide, 0.01 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.06 g (10.0 mmol) of benzaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 9 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 90.03%. The structural formula of the product is (I-10).

[0052]

[0053] Embodiment 11

[0054] 0.91 g (10.0 mmol) of thiosemicarbazide, 0.015 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.34 g (10.0 mmol) of phenylpropanaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 8 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 87.16%. The structural formula of the product is (Ⅰ-11).

[0055]

[0056] Example 12

[0057] 0.91 g (10.0 mmol) of thiosemicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 2.6 g (10.0 mmol) of hemicyssinol was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 12 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 81.26%. The structural formula of the product is (I-12).

[0058]

[0059] Example 13

[0060] 0.91g (10.0mmol) of thiosemicarbazide, 0.01g of tetrabutylammonium bromide and 30mL of deionized water were added to a 100mL three-necked flask and stirred to dissolve, and then 2.8g (10.0mmol) of magnolaldehyde was added to the system, and stirring was continued at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 12h of reaction, water was removed by rotary evaporation, and the solid product was washed three times with deionized water, filtered and dried to obtain the product with a yield of 76.27%. The structural formula of the product is (Ⅰ-13).

[0061]

[0062] Embodiment 14

[0063] 0.91g (10.0mmol) of thiosemicarbazide, 0.01g of tetrabutylammonium bromide and 30mL of deionized water were added to a 100mL three-necked flask and stirred to dissolve, then 2.84g (10.0mmol) of tofu fruit glycoside was added to the system, and stirring was continued at room temperature (25°C), and the reaction progress was tracked by thin layer chromatography. After 7h of reaction, water was removed by rotary evaporation, and the solid product was washed three times with deionized water, filtered and dried to obtain the product, with a yield of 73.78%. The structural formula of the product is (Ⅰ-14).

[0064]

[0065] Embodiment 15

[0066] 0.91 g (10.0 mmol) of thiosemicarbazide, 0.01 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 2.08 g (10.0 mmol) of sinapaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 4 h of reaction, water was removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 73.18%. The structural formula of the product is (I-15).

[0067]

[0068] Example 16

[0069] 0.75 g (10.0 mmol) of semicarbazide, 0.016 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.32 g (10.0 mmol) of cinnamaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 5 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was fully washed three times with deionized water, filtered and dried to obtain the product with a yield of 95.21%. The structural formula of the product is (Ⅰ-16).

[0070]

[0071] Embodiment 17

[0072] 0.75 g (10.0 mmol) of semicarbazide, 0.013 g of tetrabutylammonium chloride and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.2 g (10.0 mmol) of salicylaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 6 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 83.13%. The structural formula of the product is (I-17).

[0073]

[0074] Embodiment 18

[0075] Add 1.13g (15.0mmol) of semicarbazide, 0.014g of benzyltriethylammonium chloride and 45mL of deionized water to a 100mL three-necked flask and stir to dissolve, then add 0.96g (10.0mmol) of furfural to the system, continue stirring at room temperature (25°C), and track the reaction progress by thin layer chromatography. After 1h of reaction, remove water and volatile aldehydes by rotary evaporation, wash the solid product three times with deionized water, filter and dry to obtain the product, with a yield of 86.17%, and the structural formula of the product is (Ⅰ-18).

[0076]

[0077] Embodiment 19

[0078] 1.13 g (15.0 mmol) of semicarbazide, 0.010 g of benzyltriethylammonium chloride and 45 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.52 g (10.0 mmol) of citral was added to the system and continued to stir at room temperature (25 ° C). The reaction progress was tracked by thin layer chromatography. After 3 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 81.04%. The structural formula of the product is (I-19).

[0079]

[0080] Embodiment 20

[0081] 1.13 g (15.0 mmol) of semicarbazide, 0.005 g of trioctylmethylammonium chloride and 45 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.54 g (10.0 mmol) of citronellal was added to the system and continued to stir at room temperature (25 ° C). The reaction progress was tracked by thin layer chromatography. After 4 hours of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water, filtered and dried to obtain the product with a yield of 91.25%. The structural formula of the product is (Ⅰ-20).

[0082]

[0083]

[0084] Embodiment 21

[0085] 0.75 g (10.0 mmol) of semicarbazide, 0.01 g of dodecyltrimethylammonium chloride and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.5 g (10.0 mmol) of perillaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 8 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 91.63%. The structural formula of the product is (Ⅰ-21).

[0086]

[0087] Embodiment 22

[0088] 0.75 g (10.0 mmol) of semicarbazide, 0.01 g of tetradecyltrimethylammonium chloride and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 0.98 g (10.0 mmol) of trans-dihexenal was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 5 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 72.05%. The structural formula of the product is (Ⅰ-22).

[0089]

[0090] Embodiment 23

[0091] 0.75 g (10.0 mmol) of semicarbazide, 0.01 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.52 g (10.0 mmol) of vanillin was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 0.5 h of reaction, water was removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 82.74%. The structural formula of the product is (Ⅰ-23).

[0092]

[0093]

[0094] Embodiment 24

[0095] 0.75 g (10.0 mmol) of semicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.36 g (10.0 mmol) of anisaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 10 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 85.75%. The structural formula of the product is (Ⅰ-24).

[0096]

[0097] Embodiment 25

[0098] 0.75 g (10.0 mmol) of semicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.06 g (10.0 mmol) of benzaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 7 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 91.14%. The structural formula of the product is (Ⅰ-25).

[0099]

[0100] Embodiment 26

[0101] 0.75 g (10.0 mmol) of semicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 1.34 g (10.0 mmol) of phenylpropanaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 11 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 79.11%. The structural formula of the product is (Ⅰ-26).

[0102]

[0103] Embodiment 27

[0104] 0.75 g (10.0 mmol) of semicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 2.6 g (10.0 mmol) of hemicyssinol was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 8 h of reaction, water and volatile aldehydes were removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 80.25%. The structural formula of the product is (Ⅰ-27).

[0105]

[0106] Embodiment 28

[0107] 0.75 g (10.0 mmol) of semicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 2.8 g (10.0 mmol) of magnolaldehyde was added to the system and continued to stir at room temperature (25 ° C). The reaction progress was tracked by thin layer chromatography. After 5 h of reaction, water was removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 74.34%. The structural formula of the product is (Ⅰ-28).

[0108]

[0109] Embodiment 29

[0110] 0.75 g (10.0 mmol) of semicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of deionized water were added to a 100 mL three-necked flask and stirred to dissolve. Then 2.84 g (10.0 mmol) of tofu fruit glycoside was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 9 h of reaction, water was removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 68.29%. The structural formula of the product is (Ⅰ-29).

[0111]

[0112] Embodiment 30

[0113] 0.75 g (10.0 mmol) of thiosemicarbazide, 0.003 g of tetrabutylammonium bromide and 30 mL of water were added to a 100 mL three-necked flask and stirred to dissolve. Then 2.08 g (10.0 mmol) of sinapaldehyde was added to the system and continued to stir at room temperature (25°C). The reaction progress was tracked by thin layer chromatography. After 3 h of reaction, water was removed by rotary evaporation. The solid product was washed three times with deionized water and filtered and dried to obtain the product with a yield of 81.25%. The structural formula of the product is (I-30).

[0114]

[0115] Table 1 Appearance, purification method and yield of the compounds prepared in Example

[0116]

[0117]

[0118]

[0119] Embodiment 31

[0120] The biological activity of the compounds of the present invention against the southern root-knot nematode (Meloidogyne incognita) was tested by using a nematode soil column experiment. First, 250 g of soil containing nematodes was placed in a 30 cm high empty PE tube to prepare a soil column. Then, the compounds of the present invention were dissolved in DMF containing 6% Tween 80 and then diluted with deionized water to 100, 200, and 500 mg L -1, add 90 mL of the agent to the soil column, and repeat each treatment 3 times; a DMF aqueous solution containing only the same concentration of Tween 80 was used as a blank control. The soil column was placed at room temperature (25°C) for two weeks, and the death was checked under a stereo microscope and the nematode inhibition rate was calculated according to formula (1):

[0121] Inhibition rate (%) = number of nematodes in the treated soil column (pieces) / total number of nematodes in the control column (pieces) × 100% (1)

[0122] The indoor toxicity results of the compounds of the present invention to southern root-knot nematodes are shown in Table 2.

[0123] Table 2 Indoor toxicity results of the compounds of the present invention against southern root-knot nematode (Meloidogyne incognita) (100, 200, 500 mg L -1 )

[0124]

[0125]

[0126] The indoor toxicity results of the compounds of the present invention on the southern root-knot nematode (Meloidogyne incognita) show that the compounds of the present invention have a good control effect on the southern root-knot nematode. In particular, the inhibition rate (%) of sample No. I-7 can reach 87.04.

[0127] Embodiment 32

[0128] The mycelium growth rate method was used to test the inhibitory effect of the compound of the present invention on Fusarium graminearum. The compound of the present invention was dissolved in DMF containing 6% Tween 80 and diluted with deionized water to form a series of concentration gradient solutions. The drug solution was mixed with PDA culture medium to prepare a drug-carrying culture medium. A 5mm diameter bacterial cake was taken from the edge of the cultured test strain and inoculated onto the culture medium. Each treatment was repeated three times. When the colony diameter of the blank control reached about 8cm, the colony diameter was measured by the cross method, and the EC of each agent was calculated using the DPS data processing system. 50 value.

[0129] The indoor toxicity results of the compounds of the present invention against Fusarium graminearum are shown in Table 3.

[0130] Table 3 Indoor toxicity results of the compounds of the present invention against Fusarium graminearum

[0131]

[0132]

[0133] The indoor toxicity test results of the compounds of the present invention on Fusarium graminearum showed that the thiosemicarbazone compounds of the present invention had a good inhibitory effect on Fusarium graminearum. In particular, sample No. Ⅰ-4 had an EC 50 Can reach 0.31mg / L.

[0134] Embodiment 33

[0135] The mycelium growth rate method was used to test the inhibitory effect of the compound of the present invention on Botrytis cinera Pers. The compound of the present invention was dissolved in DMF containing 6% Tween 80 and diluted with deionized water to form a series of concentration gradient solutions. The drug solution was mixed with PDA culture medium to prepare a drug-carrying culture medium. A 5mm diameter bacterial cake was taken from the edge of the cultured test strain and inoculated onto the culture medium. Each treatment was repeated three times. When the colony diameter of the blank control reached about 8cm, the colony diameter was measured by the cross method, and the EC of each agent was calculated using the DPS data processing system. 50 value.

[0136] The indoor toxicity results of the compounds of the present invention against Botrytis cinera Pers are shown in Table 4.

[0137] Table 4 Indoor toxicity results of the compounds of the present invention against Botrytis cinera Pers

[0138]

[0139]

[0140] The results of the indoor toxicity test of the compounds of the present invention on Botrytis cinera Pers show that the thiosemicarbazone of the present invention has a good inhibitory effect on Botrytis cinera Pers. In particular, the EC 50 Can reach 0.06mg / L.

[0141] Embodiment 34

[0142] The mycelium growth rate method was used to test the inhibitory effect of the compounds of the present invention on Sclerotinia sclerotiorum. The compounds of the present invention were dissolved in DMF containing 6% Tween 80 and diluted with deionized water to form a series of concentration gradient solutions. The drug solution was mixed with PDA culture medium to prepare a drug-carrying culture medium. A 5mm diameter bacterial cake was taken from the edge of the cultured test strain and inoculated onto the culture medium. Each treatment was repeated three times. When the colony diameter of the blank control reached about 8cm, the colony diameter was measured by the cross method, and the EC of each agent was calculated using the DPS data processing system. 50 value.

[0143] The indoor toxicity results of the compounds of the present invention against Sclerotinia sclerotiorum are shown in Table 5.

[0144] Table 5 Indoor toxicity results of the compounds of the present invention against Sclerotinia sclerotiorum

[0145]

[0146]

[0147] The results of the indoor toxicity test of the compounds of the present invention on Sclerotinia sclerotiorum show that the thiosemicarbazone compounds of the present invention have a good inhibitory effect on Sclerotinia sclerotiorum. In particular, sample No. Ⅰ-7 has an EC 50 Can reach 1.14mg / L.

[0148] Embodiment 35

[0149] The inhibitory effect of the compound of the present invention on Ralstonia solanacearum was tested by the shake flask method. Specifically, the compound of the present invention was dissolved in DMF containing 6% Tween 80 and diluted with deionized water to form a series of solutions with a concentration gradient. The drug solution was mixed evenly with liquid LB medium in a conical flask to prepare a drug-containing medium. 1 mL (10 8 CFU) and place the conical flask in a shaker at 28-30℃, 150 rpm min -1 Each treatment was repeated three times. After 24 hours, 200uL of culture medium was taken to measure the absorbance at 600nm (OD 600 ), and the EC of each drug was calculated using the DPS data processing system 50 value.

[0150] The indoor toxicity results of the compounds of the present invention against Ralstonia solanacearum are shown in Table 6.

[0151] Table 6 Results of indoor toxicity test of the compounds of the present invention against Ralstonia solanacearum

[0152]

[0153]

[0154] The results of the indoor toxicity test of the compounds of the present invention on Ralstonia solanacearum show that the thiosemicarbazone compounds of the present invention have a good inhibitory effect on Ralstonia solanacearum. In particular, sample No. Ⅰ-7 has a good inhibitory effect on the EC of Ralstonia solanacearum. 50 Can reach 86.25mg / L.

[0155] The above is only a preferred embodiment of the present invention, and does not limit the present invention in other forms. Any technician familiar with the profession may use the above disclosed technical content to change or modify it into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the technical solution of the present invention still belongs to the protection scope of the technical solution of the present invention.

Claims

1. A compound containing a semicarbazide (thio)urea structure, characterized in that: The structural formula is shown in Formula I, ， Wherein, R1 is S, O; Wherein, R is selected from one of the following substituents: 。 2. A method for preparing a compound containing a semicarbazide (thio)urea structure according to claim 1, characterized in that: include: Step 1, adding thiosemicarbazide or semicarbazide, quaternary ammonium salt phase transfer catalyst and deionized water into a reaction container, stirring and dissolving at room temperature; Step 2, adding aldehyde-containing plant essential oil to the reaction solution of the first step, and reacting under stirring at room temperature; Step 3, the reaction product is post-treated and purified to obtain a compound containing a semicarbazide (thio)urea structure.

3. The preparation method according to claim 2, characterized in that: In step 1, the quaternary ammonium salt phase transfer catalyst is one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.

4. The preparation method according to claim 3, characterized in that: In step 1, the amount of the quaternary ammonium salt phase transfer catalyst is 1-5% of the system, and the solvent is deionized water.

5. The preparation method according to claim 2, characterized in that: In step 2, the aldehyde-containing plant essential oil is one of hemicotyl, magnolaldehyde and tofu glycoside.

6. The preparation method according to claim 5, characterized in that: In step 2, the molar ratio of the aldehyde-containing plant essential oil to thiosemicarbazide or semicarbazide is 1.0:1.0-1.

5.

7. The preparation method according to claim 2, characterized in that: In step 2, the reaction temperature is room temperature and the reaction time is 0.5 h-12 h.

8. Use of the compound containing a semicarbazide (thio)urea structure according to claim 1 in controlling soil-borne Botrytis cinerea, Sclerotinia sclerotiorum, Fusarium graminearum, Raulella fasciola and southern root-knot nematode.

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