Preparation method and application of thiocarbamido-containing norbornene compound

Abstract

The invention discloses a preparation method of a thiourea-containing norbornene compound, a product and application of the thiourea-containing norbornene compound, the structural formula of the thiourea-containing norbornene compound is shown as follows: # imgabs0 #, R: 4-F, 3-F, 4-Cl, 3-Cl, 4-Br, 4-CN, 4-CF3, 4-CH3 and 4-OCH3, and the application of the thiourea-containing norbornene compound in prevention and treatment of agricultural or forestry plant fungi is shown in the specification. An activity result shows that the compound provided by the invention has a relatively good control effect on botryosphaeria dothidea, valsa mali, sclerotinia sclerotiorum and fusarium graminearum.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticide synthesis, and particularly relates to a preparation method and application of a norbornene compound containing a thiourea group. Background Art

[0002] Trees are the backbone of forestry, defining the appearance of China's forestry and serving as the cornerstone for building ecological gardens, sponge cities, and livable cities. As people's requirements for the forestry environment in life and residence increase, the variety of tree species in forestry is also growing. The diversity of plant species brings about the diversity of pests and diseases, which can cause fatal damage to the greening and ornamental functions of trees. Currently, the use of chemical pesticides and biological pesticides is the most direct, rapid, economical, and effective means to control tree diseases. Among them, the main tree diseases include various fungal diseases such as poplar canker, walnut powdery mildew, pecan dry rot, and apple ring rot. Among them, apple ring rot is one of the forest tree diseases caused by the pathogen Botryosphaeria dothidea and has a relatively wide impact on China's apple planting industry. In the past 10-odd years, due to large-scale planting, one-sided pursuit of yield, improper management, and other reasons, many apple trees have suffered from apple ring rot. When the disease is severe, the yield in the apple planting area decreases, which has a huge impact on the increase in production and income of forest farmers. Currently, effective varieties for controlling apple ring rot include chlorothalonil, carbendazim, tebuconazole, and difenoconazole. Due to long-term and large-scale use, resistance is likely to occur. Therefore, for important forest tree diseases such as apple ring rot, the research and development trend is to develop novel-structured bactericidal agents for effective control.

[0003] Sclerotinia sclerotiorum, also known as sclerotial stem rot, is a disease that occurs in crops such as rapeseed caused by Sclerotinia sclerotiorum. This disease mainly damages the leaves, stems, flowers, pods, and seeds of rapeseed. Sclerotinia sclerotiorum is a worldwide disease, and it is most severe in the middle and lower reaches of the Yangtze River and the southeastern coastal areas of China. The incidence rate is generally 10-30%, and in severely affected fields, it can reach more than 80%. The disease not only causes a 10-70% reduction in production but also significantly reduces the oil content of the seeds of diseased plants, seriously affecting the yield and quality of rapeseed. Currently, agents for controlling Sclerotinia sclerotiorum include boscalid, dimethachlon, and tebuconazole.

[0004] On the other hand, as an important chemical intermediate, norbornene is a bridged hydrocarbon of norcamphene, with the chemical formula C 7 H 10，It is a white solid with an irritating sour taste. The molecule consists of a cyclohexene ring and a methylene bridge (between C-3 and C-6). The molecule has a double bond that causes significant ring strain and obvious reactions. Currently, norbornene is mainly used in transition metal catalysis to affect the migration of electrophilic transition metals. For example, in the research field of ring olefin ROMP, norbornene and its derivatives are the most studied and widely used type of monomer because of their high reactivity, rich sources, and low cost. In addition to studying and expanding the applicable monomers for ROMP, researchers mainly continuously try from aspects such as the steric hindrance, chemical configuration, side group polarity of norbornene-based monomers, and copolymer modification with other cycloolefins or norbornene-based monomers. At the same time, they give full play to the advantages of cycloolefin ROMP, combine it with other polymerization methods, continuously improve the performance of the obtained polymers, and apply them to different research fields. A series of research results have been obtained in the fields of flame retardant materials, exchange membranes, nanomaterials, biomedicine, etc. for norbornene and its derivatives ROMP. Among them, the research in the field of flame retardant materials started earliest and many products have been industrialized. In the field of exchange membranes, due to the good thermal stability, acid and alkali resistance, and conductivity of norbornene-based polymer membranes, the current research mainly focuses on exploring how to be applied in fuel cells. Nanomaterials are one of the hottest research fields in recent years, and preliminary applications have been made for norbornene-based nano-metal polymer materials and nano-magnetic polymer materials, etc. In the field of biomedicine, norbornene and its derivatives have great development prospects. The current research mainly focuses on drug delivery materials and preliminary research results have been obtained, but further research is still needed to achieve industrialization. Generally speaking, there are few reports on their applications in medicine or pesticides.

[0005] The preparation method and application in sterilization of the thiourea-based norbornene compounds provided by the present invention have not been reported. Summary of the Invention

[0006] The purpose of this part is to outline some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Simplifications or omissions may be made in this part, as well as in the abstract and title of the specification of this application, to avoid obscuring the purpose of this part, the abstract, and the title. However, such simplifications or omissions shall not be used to limit the scope of the present invention.

[0007] In view of the above and / or problems existing in the prior art, the present invention is proposed.

[0008] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide thiourea-based norbornene compounds.

[0009] To solve the above technical problems, the present invention provides the following technical solution: Thiourea-based norbornene compounds, and the structural formula of the thiourea-based norbornene compounds is shown as follows:

[0010]

[0011] The application of the norbornene compound containing thiourea group in controlling plant fungi in agriculture or forestry. Another object of the present invention is to overcome the deficiencies in the prior art and provide a preparation method of the norbornene compound containing thiourea group.

[0012] To solve the above technical problems, the present invention provides the following technical solution: a preparation method of the norbornene compound containing thiourea group.

[0013] Another object of the present invention is to overcome the deficiencies in the prior art and provide the application of the norbornene compound containing thiourea group in controlling plant fungi in agriculture or forestry, and the plant fungi include Botryosphaeria dothidea, Valsa mali, Sclerotinia sclerotiorum and Fusarium graminearum.

[0014] Advantages of the present invention:

[0015] (1) The norbornene compound containing thiourea group of the present invention has a novel molecular structure and is all new compounds; the chemical structure is distinct, and the structural formula contains norbornene, in which norbornene is connected by a thiourea bond; the preparation method of the compound is simple, the raw materials are easy to obtain, and the reaction conditions are easy to control. Especially in the step of synthesizing the norbornene compound containing thiourea group, the product can be obtained by beating.

[0016] (2) The compound of the present invention is a medicament for controlling plant fungi in the field of agriculture or forestry, and this medicament has good control effects on Botryosphaeria dothidea, Valsa mali, Sclerotinia sclerotiorum and Fusarium graminearum. Detailed implementation manners

[0017] To make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the specific implementation manners of the present invention will be given in conjunction with the embodiments of the specification.

[0018] Many specific details are set forth in the following description in order to fully understand the present invention, but the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar promotions without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0019] Secondly, the so-called "one embodiment" or "embodiment" herein refers to a specific feature, structure or characteristic that can be included in at least one implementation manner of the present invention. The "in one embodiment" appearing in different places in this specification does not all refer to the same embodiment, nor is it a separate or alternative embodiment that excludes other embodiments.

[0020] Example 1

[0021] Preparation of Norbornene Compounds (I-1) Containing Thiourea Group

[0022]

[0023]

[0024] Add 5-norbornene-2-methylamine (1.0 mmol), 4-fluorophenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile into a reaction flask, and react at 25 °C for 3 h. Monitor the reaction by TLC until the raw materials are completely reacted. Concentrate the reaction solution to remove anhydrous acetonitrile to obtain a crude product. Add 20 mL of n-hexane, stir for 2 h, precipitate solids, filter by suction, and dry to obtain the target compound, norbornene I-1 containing thiourea group. White powder, yield 90%. 1 H NMR(600MHz,CDCl 3 )δ7.80(s,1H),7.25–7.19(m,2H),7.15(t,J=8.3Hz,2H),6.17–5.67(m,3H),3.36(dt,J=20.8,12.4Hz,2H),2.81(s,1H),2.71(s,1H),2.42–2.24(m,1H),1.90–1.75(m,1H),1.44(d,J=7.0Hz,1H),1.24(d,J=8.2Hz,1H),0.59–0.56(m,1H).ESI-HRMS:m / z calcd.C 15 H 18 N 2 FSfor[M+H] + :277.1175,found277.1182。

[0025] Preparation of Norbornene Compounds (I-2) Containing Thiourea Group

[0026]

[0027] Add 5-norbornene-2-methylamine (1.0 mmol), 3-fluorophenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile into a reaction flask, and react at 25 °C for 2.5 h. Monitor the reaction by TLC until the raw materials are completely reacted. Concentrate the reaction solution to remove anhydrous acetonitrile to obtain a crude product. Add 20 mL of n-hexane, stir for 2 h, precipitate solids, filter by suction, and dry to obtain the target compound, norbornene I-2 containing thiourea group. White powder, yield 80%. 1 H NMR(600MHz,CDCl 3)δ8.12(s,1H),7.41(dd,J=15.2,7.2Hz,1H),7.00(dd,J=19.5,8.1Hz,3H),6.05(ddd,J=86.1,5.1,2.4Hz,3H),3.38(dd,J=25.4,3.1Hz,2H),2.79(d,J=38.5Hz,2H),2.48–2.29(m,1H),1.93–1.78(m,1H),1.45(d,J=4.1Hz,1H),1.26(d,J=8.1Hz,1H),0.62–0.59(m,1H).ESI-HRMS:m / z calcd.C 15 H 18 N 2 FSfor[M+H] + :277.1175,found 277.1179。

[0028] Preparation of norbornene compounds (I-3) containing thiourea groups

[0029]

[0030] Add 5-norbornene-2-methylamine (1.0 mmol), 4-chlorophenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile to a reaction flask, and react at 25 °C for 2 h. Monitor the reaction by TLC until the raw materials are completely reacted. Concentrate the reaction solution to remove anhydrous acetonitrile to obtain a crude product. Add 20 mL of n-hexane, stir for 2 h, precipitate a solid, filter by suction, and dry to obtain the target compound, norbornene I-3 containing thiourea groups. White powder, yield 93%. 1 H NMR(600MHz,CDCl 3 )δ7.83(s,1H),7.45(d,J=8.6Hz,2H),7.20(d,J=8.3Hz,2H),6.18(dd,J=5.6,3.0Hz,1H),5.94(dd,J=5.6,2.8Hz,1H),3.38(dt,J=21.0,12.7Hz,2H),2.85(s,1H),2.77(s,1H),2.38(ddd,J=12.2,8.3,4.2Hz,1H),1.92–1.82(m,1H),1.47(d,J=8.2Hz,1H),1.28(d,J=8.2Hz,1H),0.63–0.60(m,1H).ESI-HRMS:m / zcalcd.C 15 H 18 N 2 ClSfor[M+H] + :293.0879,found 293.0882。

[0031] Preparation of Norbornene Compounds Containing Thiourea Group (I-4)

[0032]

[0033] Add 5-norbornene-2-methylamine (1.0 mmol), 3-chlorophenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile into a reaction flask, and react at 25 °C for 2 h. Monitor the reaction by TLC until the raw materials are completely reacted. Concentrate the reaction solution to remove anhydrous acetonitrile to obtain the crude product. Add 20 mL of n-hexane, stir for 2 h, precipitate solids, filter by suction, and dry to obtain the target compound, norbornene containing thiourea group I-4. White powder, yield 95%. 1 H NMR(600MHz,CDCl 3 )δ7.98(s,1H),7.38(t,J=8.0Hz,1H),7.29(s,2H),7.12(d,J=7.4Hz,1H),6.04(ddd,J=138.8,5.6,2.9Hz,3H),3.38(dd,J=19.6,6.6Hz,2H),2.82(s,1H),2.76(s,1H),2.38(tt,J=8.0,4.0Hz,1H),1.89–1.81(m,1H),1.45(d,J=9.9Hz,1H),1.26(d,J=8.2Hz,1H),0.61–0.59(m,1H).ESI-HRMS:m / z calcd.C 15 H 18 N 2 ClSfor[M+H] + :293.0879,found 293.0885。

[0034] Preparation of Norbornene Compounds Containing Thiourea Group (I-5)

[0035]

[0036] Add 5-norbornene-2-methylamine (1.0 mmol), 4-bromophenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile into a reaction flask, and react at 25 °C for 2 h. Monitor the reaction by TLC until the raw materials are completely reacted. Concentrate the reaction solution to remove anhydrous acetonitrile to obtain the crude product. Add 20 mL of n-hexane, stir for 2 h, precipitate solids, filter by suction, and dry to obtain the target compound, norbornene containing thiourea group I-5. Light yellow powder, yield 76%. 1 H NMR(600MHz,CDCl 3)δ 7.80 (s, 1H), 7.57 (d, J = 8.5 Hz, 2H), 7.12 (d, J = 7.9 Hz, 2H), 6.03 (ddd, J = 8.4, 7.1, 4.2 Hz, 3H), 3.37 - 3.33 (m, 2H), 2.82 (s, 1H), 2.74 (s, 1H), 2.41–2.30 (m, 1H), 1.90–1.79 (m, 1H), 1.45 (d, J = 8.2 Hz, 1H), 1.25 (d, J = 8.2 Hz, 1H), 0.60–0.57 (m, 1H). ESI-HRMS: m / z calcd. C 15 H 18 N 2 BrS for [M + H] + : 337.0374, found 337.0380。

[0037] Preparation of norbornene compounds (I-6) containing thiourea groups

[0038]

[0039] Add 5-norbornene-2-methylamine (1.0 mmol), 4-cyanophenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile to a reaction flask, and react at 25 °C for 5 h. Monitor the reaction by TLC until the raw materials are completely reacted. Concentrate the reaction solution to remove anhydrous acetonitrile to obtain a crude product. Add 20 mL of n-hexane, stir for 2 h, precipitate a solid, filter by suction, and dry to obtain the target compound, norbornene I-6 containing thiourea groups. White powder, yield 70%. 1 H NMR (600 MHz, CDCl 3 )δ 8.17 (s, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.38 (s, 2H), 6.26–5.87 (m, 3H), 3.39 (s, 2H), 2.85 (s, 1H), 2.81 (s, 1H), 2.49–2.32 (m, 1H), 1.94–1.84 (m, 1H), 1.48 (d, J = 8.2 Hz, 1H), 1.28 (d, J = 8.3 Hz, 1H), 0.64–0.61 (m, 1H). ESI-HRMS: m / z calcd. C 16 H 18 N 2 S for [M + H] + : 284.1221, found 284.1229。

[0040] Preparation of norbornene compounds (I-7) containing thiourea groups

[0041]

[0042] 5-Norbornene-2-methanamine (1.0 mmol), 4-(trifluoromethyl)phenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile were added to a reaction flask, and the reaction was carried out at 25 °C for 5 h. The reaction of the raw materials was monitored by TLC until completion. The reaction solution was concentrated to remove anhydrous acetonitrile to obtain a crude product. 20 mL of n-hexane was added, and the mixture was slurried for 2 h to precipitate a solid. The solid was filtered off and dried to obtain the target compound, norbornene I-7 containing a thiourea group. It was a light yellow powder with a yield of 96%. 1 H NMR(600MHz,CDCl 3 )δ8.45(s,1H),7.69(d,J=7.4Hz,2H),7.36(s,2H),6.36–5.91(m,3H),3.39(s,2H),2.83-2.81(m,2H),2.45–2.29(m,1H),1.95–1.80(m,1H),1.46(d,J=8.3Hz,1H),1.26(d,J=8.2Hz,1H),0.62–0.59(m,1H).ESI-HRMS:m / z calcd.C 16 H 18 N 2 SF 3 for[M+H] + :327.1143,found 327.1150。

[0043] Preparation of norbornene compounds containing thiourea groups (I-8)

[0044]

[0045] 5-Norbornene-2-methanamine (1.0 mmol), 4-methylphenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile were added to a reaction flask, and the reaction was carried out at 25 °C for 2 h. The reaction of the raw materials was monitored by TLC until completion. The reaction solution was concentrated to remove anhydrous acetonitrile to obtain a crude product. 20 mL of n-hexane was added, and the mixture was slurried for 2 h to precipitate a solid. The solid was filtered off and dried to obtain the target compound, norbornene I-8 containing a thiourea group. It was a light yellow powder with a yield of 95%. 1 HNMR(600MHz,CDCl 3)δ7.69(s,1H),7.24(d,J=7.7Hz,2H),7.09(d,J=8.2Hz,2H),6.12(d,J=7.9Hz,1H),5.90(dd,J=5.5,2.7Hz,1H),3.41(dd,J=12.4,6.7Hz,1H),3.29(s,1H),2.80(s,1H),2.71(s,1H),2.38(s,3H),2.34(td,J=8.1,4.1Hz,1H),1.86–1.79(m,1H),1.42(d,J=8.1Hz,1H),1.23(d,J=8.3Hz,1H),0.58–0.56(m,1H).ESI-HRMS:m / z calcd.C 16 H 21 N 2 S for[M+H] + :273.1425,found273.1431。

[0046] Preparation of Norbornene Compounds (I-9) Containing Thiourea Group

[0047]

[0048] Add 5-norbornene-2-methylamine (1.0 mmol), 4-methoxyphenyl isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile to a reaction flask, and react at 25 °C for 1 h. Monitor the reaction by TLC until the raw materials are completely reacted. Concentrate the reaction solution to remove anhydrous acetonitrile to obtain a crude product. Add 20 mL of n-hexane, stir for 2 h, precipitate a solid, filter by suction, and dry to obtain the target compound, norbornene I-9 containing thiourea group. White powder, yield 92%. 1 H NMR(600MHz,CDCl 3 )δ7.83(s,1H),7.34(t,J=8.1Hz,1H),6.84(d,J=8.4Hz,1H),6.79(d,J=7.8Hz,1H),6.74(s,1H),6.14(dd,J=5.6,3.0Hz,1H),5.92(dd,J=5.6,2.8Hz,1H),3.82(s,3H),3.45–3.28(m,2H),2.81(s,1H),2.74(s,1H),2.41–2.32(m,1H),1.88–1.79(m,1H),1.43(d,J=9.6Hz,1H),1.24(d,J=8.2Hz,1H),0.61–0.57(m,1H).ESI-HRMS:m / z calcd.C 16 H 21 N 2OS for [M+H] + : 289.1375, found 289.1381。

[0049] Example 2

[0050] The effect of solvent on the reaction yield of 5-norbornene-2-methylamine and 4-methoxyphenyl isothiocyanate was investigated, taking the synthesis of I-9 as an example.

[0051]

[0052] The effect of solvent on the reaction yield of 5-norbornene-2-methylamine and 4-methoxyphenyl isothiocyanate was investigated. Using anhydrous acetonitrile as the solvent, the reaction yield was the highest (92%); using tetrahydrofuran as the solvent, the yield was low (71%). Therefore, acetonitrile is used as the suitable solvent for this reaction.

[0053] Example 3

[0054] Antibacterial activity (in vitro) experiment

[0055] The plant fungi used in this experiment were strains stored at 4°C in the laboratory, namely Botryosphaeria dothidea, Valsa mali, Sclerotinia sclerotiorum, and Fusarium graminearum. The medium used was potato dextrose agar medium (abbreviated as PDA). PDA medium formula: 200 g of potato (peeled), 20 g of glucose, 15 g of agar, 1000 mL of distilled water. Preparation method: Wash and peel the potato, weigh 200 g and cut into small pieces, add water and boil until soft (boil for 20 - 30 minutes until it can be pierced with a glass rod), filter through eight layers of gauze into a beaker, add 15 - 20 g of agar according to the experimental needs, add 20 g of glucose, stir evenly, fully dissolve and then cool slightly, make up the volume to 1000 mL with water, dispense and sterilize at 121°C for 15 minutes, and reserve after cooling.

[0056] Experimental method: The growth rate method was adopted.

[0057] (1) First, culture 7 plant fungi on PDA plates at 25°C for about 3 - 6 days for later use;

[0058] (2) Heat and melt the PDA medium, cool it to 45 - 50°C, add 250 μL of the test compound at a concentration of 10 g / L to make a medium containing 50 mg / L of the medicinal solution, and pour it into petri dishes and cool. Chlorothalonil was used as the positive control;

[0059] (3) Under aseptic operation, use a punch to punch out circular mycological disks (diameter 0.50 cm) at the edge of the mycelia of each strain cultured for 6 days (with as consistent growth status as possible), then use an inoculation needle to pick them to the center of the drug-containing plate, and then place the petri dishes upside down in an incubator (28°C) for culture;

[0060] (4) Observe and measure the growth of hyphae at different times after treatment, measure the diameter using the cross method and process the data to calculate the inhibition rate;

[0061] (5) Inhibition rate (%) = (control hypha diameter - treated hypha diameter) / (control hypha diameter - 0.5) × 100;

[0062] (6) Each treatment is repeated 3 times.

[0063] Table 1 Test results of the inhibitory activities of norbornene compounds containing thiourea groups against four plant pathogenic fungi

[0064] a Note: Each treatment in the experiment was set with three replicates, and the data in the table are the averages of three replicates.

[0065] Table 1 Activities (inhibition rate / %) of norbornene compounds containing thiourea groups against four plant pathogenic fungi Table 2 EC of some compounds 50

[0066]

[0067] The bactericidal activity determination results of experimental group I and the control agent chlorothalonil are shown in Table 1 and Table 2. From the results in Table 1

[0068] It can be seen that at a concentration of 50 mg / L, the compounds in series I showed varying degrees of bactericidal activity against 4 plant fungi. The inhibition rate of compound I-6 against Sclerotinia sclerotiorum was 100%, which was better than that of chlorothalonil; the inhibition rates of compounds I-2, I-8, and I-9 against Valsa mali were over 90%, which was better than that of chlorothalonil; the inhibition rate of compound I-6 against Botryosphaeria dothidea was 92%, which was better than that of chlorothalonil.

[0069] In view of the good inhibitory activity of the target compounds against several plant pathogens, the EC 50 values of the compounds with higher inhibition rates in the preliminary screening were tested. The EC 50 of the compounds are listed in Table 2. It can be seen that the EC 50 of compound I-6 against Sclerotinia sclerotiorum was 3.69 mg / L, and the EC 50 of compound I-8 against Sclerotinia sclerotiorum was 5.40 mg / L, which was better than that of chlorothalonil (12.30 mg / L). In addition, the EC 50 value of compound I-6 against Botryosphaeria dothidea was 9.51 mg / L, which was at the same level as the positive control chlorothalonil. The compounds in series I had good inhibitory activity against several fungi and had the potential to develop antifungal agents.

[0070] The thiourea group-containing norbornene compounds of the present invention have distinct structural differences and distinct chemical structural characteristics, and show good effects against Botryosphaeria dothidea, Valsa mali, Sclerotinia sclerotiorum and Fusarium graminearum. They can be used to control fungal diseases of agricultural or forestry plants. The preparation method of the compounds is simple, the yield is relatively high, and the product properties are stable.

[0071] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing a thiourea-containing norbornene compound, characterized in that: The structural formula of the thiourea-containing norbornene compound is as follows: Among them: R: 4-F, 3-F, 4-Cl, 3-Cl, 4-Br, 4-CN, 4-CF3, 4-CH3, 4-OCH3.

2. The method for preparing a thiourea-containing norbornene compound according to claim 1, characterized in that: include, Add 5-norbornene-2-methylamine (1.0 mmol), substituted isothiocyanate (1.0 mmol) and 10 mL of anhydrous acetonitrile to the reaction bottle, react at 25 ° C for 1-5 h, monitor the reaction of the raw materials by TLC, concentrate the reaction solution to remove anhydrous acetonitrile to obtain a crude product, add 20 mL of n-hexane, beat for 2 h, precipitate solids, filter and dry to obtain the target compound, a thiourea-containing norbornene compound.

3. The method for preparing a thiourea-containing norbornene compound according to claim 2, characterized in that: The molar ratio of the intermediate substituted 5-norbornene-2-methylamine to the substituted phenyl isothiocyanate is 1.0:

1.

4. The method for preparing a thiourea-containing norbornene compound according to claim 2, characterized in that: The thiourea-containing norbornene compounds I-1 to I-9 are synthesized, wherein the synthesis reaction temperature is 25° C. and the reaction time is 1-5 h.

5. An application of a thiourea-containing norbornene compound, characterized in that: The application of the thiourea-containing norbornene compound in preventing and controlling plant pathogenic fungi in agriculture or forestry.

6. The use according to claim 5, characterized in that: The plant pathogenic fungi include Botrytis cinerea, apple rot fungus, rapeseed sclerotinia and Fusarium graminearum.

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