Preparation and application of disulfide cyclopentenone derivative

Abstract

The invention discloses preparation and application of a disulfide cyclopentenone derivative, and belongs to the technical field of organic synthesis. The chemical structural formula of the dithiocyclopentenone derivative provided by the invention is as shown in formula (I): # imgabs0. The compound is used for preventing and treating plant pathogenic fungi, and particularly has high activity on magnaporthe oryzae.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to the preparation and application of dithiocyclopentenone derivatives. Background Art

[0002] Plant diseases seriously threaten the safety and stability of crop production. Effective prevention and control of plant diseases is crucial to achieving high crop yields. Currently, many fungicides with high efficiency, low toxicity and broad spectrum are widely used to reduce plant diseases in agriculture. However, due to long-term and frequent use, fungicides not only leave pesticide residues in agricultural products, but also cause plant pathogens to develop resistance. Therefore, the development of fungicides with novel modes of action, low residues and no resistance is crucial to the development of global agriculture. Summary of the invention

[0003] In view of the above technical problems, the present invention provides a preparation method and application of dithiocyclopentenone derivatives.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] Technical purpose 1: A dithiocyclopentenone derivative, the chemical structure of which is shown in formula (I): Wherein, R1 is selected from phenyl or substituted phenyl, pyridyl, thiazolyl, thienyl or piperazinyl; R2 is selected from H, -CH3 or -CH2CH3.

[0006] Technical purpose 2: A method for preparing dithiocyclopentenone derivatives, comprising the following steps:

[0007] Will Anhydrous potassium carbonate and tetrahydrofuran are stirred in an ice-water bath, and then dichloro-1,2-dithiocyclopentenone is added and reacted at room temperature to obtain an intermediate;

[0008] The intermediate is dissolved in acetonitrile, and iodotrimethylsilane is added. The reaction is carried out under nitrogen and room temperature. The reaction is stopped after the raw materials react completely. Saturated sodium bicarbonate solution and dichloromethane are continuously added dropwise to the reaction product for extraction. The organic phases are combined, and finally back-extracted once with sodium thiosulfate, dried, concentrated under reduced pressure, and subjected to column chromatography to obtain dithiocyclopentenone derivatives.

[0009] Furthermore, the The molar ratio of anhydrous potassium carbonate and dichloro-1,2-dithiocyclopentenone is 1:2:2;

[0010] Said The usage ratio of tetrahydrofuran is 1g:40mL.

[0011] Further, the molar ratio of the intermediate to iodotrimethylsilane is 1:4;

[0012] The usage ratio of the intermediate and acetonitrile is 0.3 g:10 mL.

[0013] Technical purpose three: An application of the dithiocyclopentenone derivatives in controlling and eliminating pathogens of plant diseases, wherein the pathogens refer to pathogenic fungi.

[0014] Technical purpose four: A fungicide comprising 1-95wt% of dithiocyclopentenone derivatives.

[0015] Furthermore, the fungicide also includes a surfactant and a carrier that are acceptable in pesticides.

[0016] Furthermore, the fungicide is in the form of a pesticide-acceptable water-dispersible powder, suspension, granule, dry suspension, emulsifiable concentrate, aqueous solution, oil, fumigant, aerosol or microcapsule.

[0017] Technical purpose 5: An application of the fungicide in controlling and eliminating pathogens of plant diseases, wherein the pathogens refer to pathogenic fungi.

[0018] Technical purpose six: A sterilization method, applying the fungicide to seeds, plants, fruits or growing soil.

[0019] The core innovation of the present invention is that benzene rings and phenyl-type amine compounds undergo nucleophilic substitution with dichloro-1,2-dithiocyclopentenone to obtain an intermediate, and the intermediate is then dechlorinated and reduced to hydrogen by iodosilane to obtain a new dithiocyclopentenone derivative. Through skeleton migration and bioelectronic isostery, dithiocyclopentenone compounds with the same carbon skeleton are constructed, and hydrogen is introduced into the pharmacophore structure. Compounds with this structure have excellent antibacterial activity and a unique mechanism of action, which makes it difficult to produce cross-resistance with fungicides of other mechanisms and has a high antibacterial rate.

[0020] Compared with the prior art, the present invention has the following advantages and technical effects:

[0021] The dithiocyclopentenone derivatives of the present invention have high activity against rice blast fungus, and the maximum antibacterial rate against rice blast fungus can reach 97.9% at a concentration of 100 ppm.

[0022] The dithiocyclopentenone derivatives of the present invention can be used to prepare fungicides of various formulations for controlling and eliminating pathogenic fungi of plant diseases. DETAILED DESCRIPTION

[0023] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0024] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0025] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0026] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0027] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0028] The term "active substance of the present invention" or "active compound of the present invention" refers to the dithiocyclopentenone derivatives of the present invention, which have high antibacterial activity.

[0029] A dithiocyclopentenone derivative, the chemical structure of the compound is shown in formula (I): Wherein, R1 is selected from phenyl, pyridyl, thiazolyl, thienyl or piperazinyl; R2 is selected from H, -CH3 or -CH2CH3.

[0030] The preparation method of the dithiocyclopentenone derivatives and the chemical synthesis method are as follows:

[0031]

[0032] The specific steps include:

[0033] (1) Anhydrous potassium carbonate and tetrahydrofuran are stirred in an ice-water bath, and then dichloro-1,2-dithiocyclopentenone is added and reacted at room temperature to obtain an intermediate;

[0034] (2) The intermediate is dissolved in acetonitrile, iodotrimethylsilane is added, and the reaction is carried out under nitrogen and room temperature. After the raw materials react completely, the reaction is stopped, and saturated sodium bicarbonate and dichloromethane are added dropwise to the reaction product for extraction. The organic phases are combined, and finally, sodium thiosulfate is used for back extraction once, and the mixture is dried, concentrated under reduced pressure, and subjected to column chromatography to obtain dithiocyclopentenone derivatives.

[0035] In the following preferred embodiments of the present invention, The molar ratio of anhydrous potassium carbonate to dichloro-1,2-dithiocyclopentenone is 1:2:2; The molar ratio of the intermediate to tetrahydrofuran is 1 g:40 mL; the molar ratio of the intermediate to iodotrimethylsilane is 1:4; and the molar ratio of the intermediate to acetonitrile is 0.3 g:10 mL.

[0036] The dithiocyclopentenone derivatives are used in controlling and eliminating pathogenic bacteria of plant diseases, wherein the pathogenic bacteria refer to pathogenic fungi.

[0037] The active substance of the present invention can be used to control and eliminate pathogenic fungi that cause plant diseases, and can be used for crop protection, wherein the crops are cereals, corn, rice, soybeans and other leguminous plants, fruits and fruit trees, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceous plants, oil plants, tobacco, coffee, tea, cocoa, beets, sugarcane, cotton, potatoes, tomatoes, onions, peppers and other vegetables, and ornamental plants. The "pathogen" in this specification refers to a pathogenic fungus that is a plant disease. Specifically, for example, the following plant diseases caused by pathogens can be cited, but the specific examples are not limited to these.

[0038] Examples include rice blast (Pricuaria oryzae), rice flax spot (Helminthosporium oryzae), cereal powdery mildew (Erysiphe graminis), wheat head blight (Fusarium graminearum), wheat leaf blight (Septoria tritici), citrus black spot (Phomaci tricarpa), citrus anthracnose (Colletrichum gloeosporioides), apple blossom rot (Sclerotinia mali), apple powdery mildew (Podosphaeraleucotricha), apple leaf spot (Alternaria mali), pear scab (Vnturia pirina), pear rust (Gymnosporangium haraenum), peach anthracnose (Gloeosporium laelicolor), nuclear anthracnose (Gloeosporium laeticolor), grape downy mildew (Plasmopara viticola), grape black pox (Sphaceloma ampelinum), grape anthracnose (Glomerella cingulala), cucumber downy mildew (Pseudoperonospora cubensis), melon anthracnose (Colletotrichum lagenarium), cucumber powdery mildew (Sphaerothecafuliginea), cucumber vine blight (Mycosphaerella melonis), cucumber gray disease (Botrytis cinerea), tomato early blight (Altermaria solani), tomato leaf mold (Cladosporium fiuvum) and late blight (Phytophthora infestans), crucifer black spot (Alternaria brassicae), rape white spot (Ceroosporella brassicae), flax anthracnose (Cilletotrichum boehmieriae), peanut black spot (Mycosphaerella personatu), brown spot (Cercospora arachidicola), potato late blight (Phytophthora infestans), strawberry powdery mildew (Sphaerothecahumuli), tobacco powdery mildew (Erysiphe cichoraoearm), anthracnose (Colletotrichum nicotianae), beet brown spot (Cercospora beticola),Rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), cassava brown spot (Cercospora vicosae), cassava anthracnose (Colletotrichum gloeosporioides), litchi downy mildew (Peronophthora litchic), fragrant leaf spot (Cercospora musae), banana anthracnose (Gioeosporium musarum), papaya anthracnose (Colletotrichum gloeosporioides; Colletotrichum capsici), fruit anthracnose (Colletotrichumgloeosporioides) and other plant diseases.

[0039] A more preferred disease to which the fungicide of the present invention can be applied is rice blast.

[0040] A fungicide prepared by using the above dithiocyclopentenone derivatives, comprising 1-95wt% of dithiocyclopentenone derivatives as active ingredients, and the remaining components are pesticide-acceptable adjuvants and carriers, wherein the adjuvants include surfactants, adhesives, dispersants, stabilizers and other preparations.

[0041] The dosage form of the fungicide is a water-dispersible powder, suspension, granule, dry suspension, emulsifiable concentrate, aqueous solution, oil, fumigant, aerosol or microcapsule acceptable in pesticide science. These preparations can be prepared by a common method. For example, the active substance is mixed with a liquid solvent and / or a solid carrier, and a surfactant, emulsifier, dispersant, stabilizer, wetting agent is added at the same time, and an adhesive, dye or flavoring agent can also be added.

[0042] As the surfactant, optional nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene fatty acid (mono or di) ester, sorbitan fatty acid ester, castor oil ethylene oxide adduct, acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, alkyl glycosides, etc.; anionic surfactants include alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, salts of formalin condensates of naphthalenesulfonic acid, salts of formalin condensates of alkylnaphthalenesulfonic acid, polyoxyethylene alkyl ether sulfuric acid or phosphate ester salts, polyoxyethylene (mono or di) alkylphenyl ether sulfuric acid or phosphate ester salts, polycarboxylates (such as polyacrylates, polymaleates, and copolymers of maleic acid and olefins, etc.), polystyrene sulfonates, etc.; cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts; amphoteric surfactants such as amino acid type and betaine type; silicone surfactants, fluorine surfactants, etc.

[0043] As the binder or dispersant, casein, gelatin, various types (starch, arabic resin, fiber derivatives, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers, etc. can be selected.

[0044] As the stabilizer, optional ones include acidic isopropyl phosphate vegetable oil, mineral oil, fatty acid, etc.

[0045] The carrier can be a liquid carrier and / or a gaseous carrier. Suitable solid carriers include natural and synthetic clays, silicates, such as natural silica and diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as activated tantalum and vermiculite; aluminum silicates, such as kaolinite, montmorillonite, mica; calcium carbonate, calcium sulfate, ammonium sulfate; synthetic hydrated silicon oxide and synthetic calcium silicate or aluminum silicate. Particularly suitable solid carriers for powders include naturally occurring rock powders, such as attapulgite, bentonite, montmorillonite, diatomaceous earth; synthetic ground minerals, such as micro-dispersed silicic acid or aluminum oxide. Particularly suitable carriers for granules include broken and graded natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic particles made from organic and inorganic powders. In addition, particles can be prepared from organic materials, such as sawdust, peanut shells, corn cob fibers and dried tobacco stems.

[0046] Suitable liquid carriers include water: water can be used as a solvent or diluent, and organic solvents can also be used as auxiliary solvents or antifreeze additives. Suitable organic solvents include aromatic hydrocarbons, such as toluene, xylene, benzene, phenyl alkyl naphthalene and chlorinated aromatic hydrocarbons; chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride, trichloroethane, methylene chloride, chloroform, carbon tetrachloride and polychlorinated ethanes; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, light mineral oil and paraffin; however, particularly suitable are polar solvents, i.e. alcohols, such as isopropanol, butanol, ethylene glycol, benzyl alcohol, furfuryl alcohol, cyclohexanol, ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butyrolactone, dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone. Mixtures of different liquids are often suitable.

[0047] These solid and liquid carriers may be used alone or in combination of two or more.

[0048] By adding one or more other fungicides to the composition, it can have a broader spectrum of activity than the compound of general formula (I) alone. In addition, other fungicides can have a synergistic effect on the antibacterial activity of the compound of general formula (I). The compound of general formula (I) can also be mixed with other insecticides, or mixed with another fungicide and other insecticides at the same time. Since the active compound itself is active, it can also be used alone.

[0049] The amount of active ingredient in the fungicide of the present invention is generally preferably 1-90wt% relative to the overall preparation. When the active ingredient of the present invention is used as a fungicide, the application rate can vary in a relatively wide range, depending on the type of application. The application rate of the active ingredient of the present invention is: when treating plant parts, such as leaves: 0.1-10000g / ha, preferably 10-1000g / ha, more preferably 50-300g / ha (when applied in the form of irrigation or drip irrigation, the application rate can even be reduced, especially when using inert materials such as rock wool or perlite); when treating seeds: 2-200g per 100kg seeds, preferably 2.5-150g per 100kg seeds, more preferably 2.5-25g per 100kg seeds, even more preferably 2.5-12.5g per 100kg seeds; when treating soil: 0.1-10000g / ha, preferably 1-5000g / ha.

[0050] The method for preparing fungicides of different dosage forms using the dithiocyclopentenone derivatives of the present invention can be a conventional method, such as:

[0051] 1) Wettable powder fungicide: Prepare the following components in proportion: 30% (weight percentage, the same below) of any one of the compounds in the Compound I series; 2% sodium dodecyl sulfate; 3% sodium lignin sulfonate; 5% naphthalenesulfonic acid formaldehyde condensate and 60% light calcium carbonate. Mix the components thoroughly, and grind them with an ultrafine grinder to obtain a 30% wettable powder fungicide.

[0052] 2) Suspension fungicide: Prepare the following components in proportion: 40% of any one of the compounds in the Compound I series; 10% of ethylene glycol; 6% of nonylphenol polyglycol ether; 5% of sodium lignin sulfonate; 1% of carboxymethyl cellulose; 0.2% of formaldehyde aqueous solution (37%); 0.8% of silicone oil water emulsion water (75%) and 37% of water. Mix the components thoroughly to obtain a 40% suspension fungicide.

[0053] 3) Water-dispersible granular fungicide: Prepare the following components in proportion: 60% of any compound in Compound I series; 12% of naphthalenesulfonic acid formaldehyde condensate; 8% of sodium N-methyl-N-oleoyl-taurate; 2% of polyvinyl pyrrolidone; 2% of carboxymethyl cellulose and 16% of kaolin. Mix the components and grind them, add water and knead them, add them into a granulator with a 10-100 mesh screen for granulation, and then dry and sieve them to obtain a 60% water-dispersible granular fungicide.

[0054] The wettable powder or water-dispersible granules thus obtained can be used by diluting with water to a predetermined concentration to prepare a solution, suspension or emulsion and then spraying it on plants.

[0055] The bactericide prepared by the present invention is used in controlling and eliminating pathogenic bacteria of plant diseases, wherein the pathogenic bacteria refers to pathogenic fungi.

[0056] The sterilization method refers to applying the fungicide to seeds, plants, fruits or growing soil.

[0057] The "room temperature" in the present invention refers to 20-30°C unless otherwise specified.

[0058] The raw materials used in the present invention are all purchased from the market.

[0059] The technical solution of the present invention is further illustrated by the following embodiments.

[0060] The synthetic route is as follows:

[0061]

[0062] Example 1

[0063] Synthesis of Compound I1 (R1 = 3-F-phenyl; R2 = H)

[0064] Add 3-fluorobenzylamine (1g, 7.99mmol), anhydrous potassium carbonate (2.21g, 15.98mmol), 40mL dry tetrahydrofuran to a 150mL round-bottom flask, stir in an ice-water bath for 10min, then slowly add dichloro-1,2-dithiocyclopentenone (2.99g, 15.99mmol) to the mixture, remove the ice bath, react at room temperature, and monitor the reaction by TLC. After the raw material reacts completely, stop the reaction, filter, concentrate and distill under reduced pressure. Column chromatography separation (V (dichloromethane): V (methanol) = 5: 1) obtains 0.5g of the intermediate 4-chloro-5-((3-fluorobenzyl)amino)-3H-1,2-dithiol-3-one.

[0065] The intermediate (0.30 g, 1.09 mmol) was dissolved in 10 mL of acetonitrile and placed in a 50 mL three-necked flask, and iodotrimethylsilane (0.87 g, 4.35 mmol) was added. The reaction was carried out at room temperature under nitrogen protection, and the progress of the reaction was detected by TLC. After the reaction of the raw materials was complete, the reaction was stopped; then 10 mL of saturated sodium bicarbonate was added dropwise to the mixed solution, and 20 mL of dichloromethane was used for extraction three times, and the organic phases were combined, and finally sodium thiosulfate was used for back extraction once. After drying over anhydrous sodium sulfate, it was concentrated under reduced pressure, and the target compound was obtained as a brown oil by column chromatography (petroleum ether: ethyl acetate = 3:1), and the yield was 76.9%. 1H NMR(400MHz, CDCl3)δ7.59(s,-NH,1H),7.33(t,J=7.5Hz,Ph-H,1H),7.24(dt,J=7.5,1.1Hz,Ph-H,1H), 7.03(dt,J=7.3,2.0Hz,Ph-H,1H),6.98-6.96(m,Ph-H,1H),5.59(s,=CH-,1H),4.53(s,Ph-CH2-N,2H); 13 C NMR (101MHz, CDCl3) δ189.46,168.56,164.91,138.03,132.19,128.60,118.02,117.84,112.58,48.15.

[0066] Example 2

[0067] Synthesis of compound I2 (R1 = phenyl; R2 = H)

[0068] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as a brown oil with a yield of 80.8%. 1 H NMR (400MHz, CDCl3) δ7.42 (s, -NH, 1H), 7.32 (d, J = 0.8Hz, Ph-H, 2H), 7.31-7.28 ( m,Ph-H,2H),7.27-7.23(m,Ph-H,1H),5.59(s,=CH-,1H),4.49(s,Ph-CH2-N,2H). 13 CNMR(101MHz)δ189.46,166.61,143.58,132.39,131.28,131.12,112.58,52.08.

[0069] Example 3

[0070] Synthesis of Compound I3 (R1 = 3-Cl-phenyl; R2 = H)

[0071] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as a yellow solid with a yield of 72.7%. mp = 117.5-118.6°C 1 H NMR (400MHz, CDCl3) δ7.59(s,-NH-,1H),7.30-7.23(m,Ph-H,4H),5.59(s,=CH-,1H),4.58(s,Ph-CH2-N,2H); 13CNMR(101MHz, CDCl3)δ189.46,167.79,139.13,135.95,132.28,131.74,131.07,130.84,112.58,51.33.HRMS(ESI+):calcd forC 10 H9ClNO2S2(M+H) + 257.9808,found,257.9809.

[0072] Example 4

[0073] Synthesis of compound I4 (R1 = 3-CN-phenyl; R2 = H)

[0074] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a pale yellow powder with a yield of 69.7%. mp = 69.2-70.1℃. 1 H NMR (400MHz, CDCl3) δ7.59 (s, -NH, 1H), 7.67 (d, J = 1.1Hz, Ph-H, 1H), 7.56-7.52 ( m,Ph-H,1H),7.35-7.30(m,Ph-H,2H),5.59(s,=CH-,1H),4.51(s,Ph-CH2-N,2H); 13 C NMR (101MHz, CDCl3) δ189.46,167.79,138.67,136.11,133.83,132.00,130.64,120.11,113.18,112.58,51.65.

[0075] Example 5

[0076] Synthesis of Compound I5 (R1=3,5-(OCH3)2-phenyl;R2=H)

[0077] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a beige white powder with a yield of 40.3%. mp = 130.9-131.1℃. 1 H NMR (400MHz, CDCl3) δ7.54 (s, -NH, 1H), 6.66 (dt, J = 2.0, 1.0Hz, Ph-H, 2H), 6.41 (t, J =2.0Hz,Ph-H,1H),5.59(s,=CH-,1H),4.44(s,Ph-CH2-N,2H),3.81(s,Ph-OCH3,6H); 13C NMR (101MHz, CDCl3) δ189.46,168.08,161.91,138.49,112.58,108.99,100.51,56.17,48.68.

[0078] Example 6

[0079] Synthesis of Compound I6 (R1=4,5-(OCH3)2-phenyl;R2=H)

[0080] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a light yellow solid with a yield of 72.9%. mp = 101.0-101.5°C. 1 H NMR (400MHz, CDCl3) δ7.60 (s, -NH, 1H), 6.86 (d, J = 1.0Hz, Ph-H, 1H), 6.84 (d, J = 7.4Hz, Ph-H, 1H), 6.82-6. 79(m,Ph-H,1H),5.59(s,=CH-,1H),4.48(s,Ph-CH2-N,2H),3.85(s,Ph-OCH3,3H),3.83(s,Ph-OCH3,3H); 13 C NMR (101MHz, CDCl3) δ189.46,168.98,150.53,150.23,132.37,123.58,112.58,112.26,112.25,56.50,56.49,50.25.

[0081] Example 7

[0082] Synthesis of Compound I7 (R1 = 2,4-(OCH3)2-phenyl; R2 = H)

[0083] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as an orange-yellow solid with a yield of 40.8%. mp = 84.6-85.1°C. 1 H NMR (400MHz, CDCl3) δ7.45 (s, -NH, 1H), 7.16 (dt, J=7.5, 1.0Hz, Ph-H, 1H), 6.68 (dd, J=7.5, 2.0Hz, Ph-H, 1H), 6.4 4(d,J=2.0Hz,Ph-H,1H),5.59(s,=CH-,1H),4.58(s,Ph-CH2-N,2H),3.83(s,Ph-OCH3,3H),3.80(s,Ph-OCH3,3H); 13C NMR(101MHz, CDCl3)δ189.46,165.47,162.51,161.68,132.45,121.87,111.71,107.75,99.41,56.29,56.24,50.02.HRMS(ESI+):calcd for C 12 H 14 NO3S2(M+H) + 284.0409,found,284.0410.

[0084] Example 8

[0085] Synthesis of Compound I8 (R1=2,3-(OCH3)2-phenyl;R2=H)

[0086] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a light yellow powder with a yield of 83.3%. mp = 137.4-137.9℃. 1 H NMR (400MHz, CDCl3) δ7.53 (s, -NH, 1H), 7.01-6.96 (m, Ph-H, 1H), 6.88 (t, J = 7.5Hz, Ph-H, 1H), 6.82 (dd, J = 7. 5,2.0Hz,Ph-H,1H),5.59(s,=CH-,1H),4.48(s,Ph-CH2-N,2H),3.84(s,Ph-OCH3,3H),3.84(s,Ph-OCH3,3H); 13 C NMR (101MHz, CDCl3) δ189.46,164.13,150.23,150.01,128.73,124.25,123.76,114.02,111.71,61.24,56.53,48.97.

[0087] Example 9

[0088] Synthesis of Compound I9 (R1 = 4-F-phenyl; R2 = H)

[0089] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as an orange powder with a yield of 67.4%. mp = 139.1-140.5°C 1 H NMR (400MHz, CDCl3) δ7.42(s,-NH,1H),7.31(dt,J=7.5,1.1Hz,Ph-H,2H),7.08-7.05(m,Ph-H,2H),5.59(s,=CH-,1H),4.46(s,Ph-CH2-N,2H); 13CNMR (101MHz, CDCl3) δ189.46,166.61,164.46,137.76,132.22,132.22,116.97,116.97,112.58,51.72.

[0090] Example 10

[0091] Synthesis of Compound I10 (R1 = 3-OCH3-phenyl; R2 = H)

[0092] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as a beige white powder with a yield of 76.9%. mp = 96.7-97.3°C 1 H NMR (400MHz, CDCl3) δ7.68(s,-NH-,1H),7.25(t,J=7.7Hz,Ph-H,1H),7.19(dtt,J=7.5,1.9,1.0Hz,Ph-H,1H),6.87 (d,J=2.0Hz,Ph-H,1H),6.86(q,J=2.0Hz,Ph-H,1H),5.59(s,=CH-,1H),4.46(s,Ph-CH2-N,2H),3.80(s,-OCH3,3H); 13 C NMR(101MHz, CDCl3)δ189.46,168.56,161.36,139.52,131.44,125.50,116.27,113.40,112.58,56.01,49.96.HRMS(ESI+):calcd for C 11 H 12 NO2S2(M+H) + 254.0302,found,254.0304.

[0093] Embodiment 11

[0094] Synthesis of Compound I11 (R1=5,6-F-phenyl;R2=H)

[0095] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as an orange-yellow solid with a yield of 90.5%. mp = 96.3-97.0℃. 1 H NMR (400MHz, CDCl3) δ7.42(s,-NH,1H),7.23(s,Ph-H,1H),7.22(s,Ph-H,1H),7.17-7.13(m,Ph-H,1H),5.59(s,=CH-,1H),4.38(s,Ph-CH2-N,2H); 19FNMR (565MHz, CDCl3) δ-136.95 (d, J=20.9Hz, 1F), -142.82 (d, J=20.3Hz, 1F). 13 C NMR(101MHz, CDCl3)δ189.46,164.86,151.66,150.66,128.48,127.84,123.82,117.24,111.71,50.13.HRMS(ESI+):calcd for C 10 H8F2NOS2(M+H) + 260.0009,found,260.0010.

[0096] Example 12

[0097] Synthesis of Compound I12 (R1 = 3,6-Cl-phenyl; R2 = H)

[0098] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as an orange-yellow powder with a yield of 78.1%. mp = 86.7-87.9°C. 1 H NMR (400MHz, CDCl3) δ7.40(s,-NH,1H),7.38-7.35(m,Ph-H,1H),7.25(d,J=7.4Hz,Ph -H,1H),7.21(dd,J=7.5,2.0Hz,Ph-H,1H),5.59(s,=CH-,1H),4.54(s,Ph-CH2-N,2H); 13 C NMR (101MHz, CDCl3) δ189.46,167.17,135.27,134.87,133.24,132.14,131.42,130.82,111.45,49.82.

[0099] Example 13

[0100] Synthesis of compound I13 (R1 = 4-N(CH3)2-phenyl; R2 = H)

[0101] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a brown-yellow powder with a yield of 52.0%. mp = 136.0-136.5°C. 1H NMR (400MHz, CDCl3) δ7.42(s,-NH,1H),7.21(t,J=1.0Hz,Ph-H,1H),7.20(t,J=1.1Hz,Ph-H,1H),6.71(d,J=1.6 Hz,Ph-H,1H),6.70(d,J=1.6Hz,Ph-H,1H),5.59(s,=CH-,1H),4.45(s,Ph-CH2-N,2H),2.95(s,Ph-N(CH3)2,6H); 13 CNMR (101MHz, CDCl3) δ189.46,166.61,152.01,137.45,131.36,115.26,112.58,51.74,41.19.

[0102] Embodiment 14

[0103] Synthesis of compound I14 (R1 = 4-OCH3-phenyl; R2 = H)

[0104] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as a beige white solid with a yield of 76.9%. mp = 158.1-158.3°C 1 H NMR (400MHz, CDCl3) δ7.42(s,-NH,1H),7.20(t,J=1.0Hz,Ph-H,1H),7.18(t,J=1.0Hz,Ph-H,1H),6.89(d,J=1. 6Hz,Ph-H,1H),6.88(d,J=1.5Hz,Ph-H,1H),5.59(s,=CH-,1H),4.46(s,Ph-CH2-N,2H),3.79(s,Ph-OCH3,3H); 13 C NMR(101MHz, CDCl3)δ189.46,166.61,161.44,136.01,131.47,131.47,115.68,115.68,112.58,56.03,51.72.HRMS(ESI+):calcd for C 11 H 12 NO2S2(M+H) + 254.0302,found,254.0304.

[0105] Embodiment 15

[0106] Synthesis of compound I15 (R1 = 3-CN-phenyl; R2 = -CH3)

[0107] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as a beige solid with a yield of 57.7%. mp = 69.2-71.9°C 1 H NMR (400MHz, CDCl3) δ7.54 (dt, J=7.5, 2.0Hz, Ph-H, 1H), 7.49 (dp, J=1.9, 0.9Hz, Ph-H, 1H), 7.36 (d, J=14.9Hz, Ph-H,1H),7.27(d,J=7.5Hz,Ph-H,1H),5.58(s,=CH-,1H),4.51(t,J=1.0Hz,Ph-CH2-N,2H),3.15(s,-CH3,3H); 13 C NMR (101MHz, CDCl3) δ189.50,162.98,138.74,136.14,133.83,131.56,130.70,120.11,113.54,108.98,58.38,40.98.

[0108] Example 16

[0109] Synthesis of compound I16 (R1 = phenyl; R2 = -CH3)

[0110] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a light yellow solid with a yield of 88.0%. mp = 103.6-104.2℃. 1 H NMR (400MHz, CDCl3) δ7.43-7.32(m,Ph-H,3H),7.26-7.20(m,Ph-H,2H),5.57(s,=CH-,1H),4.61(s,Ph-CH2-N,2H),3.11(s,-CH3,3H). 13 C NMR (101MHz, CDCl3) δ189.22,173.86,134.62,129.16,128.39,127.12,93.08,58.03,39.87.

[0111] Embodiment 17

[0112] Synthesis of Compound I17 (R1 = 3-Cl-phenyl; R2 = -CH3)

[0113] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a beige solid with a yield of 92.3%. mp = 72.6-73.3°C. 1H NMR (400MHz, CDCl3) δ7.33 (dd, J=2.6, 1.2Hz, Ph-H, 1H), 7.32 (d, J=1.3Hz, Ph-H, 1H), 7.21 (dt, J=2.5, 1.1Hz, Ph -H,1H),7.12(dtd,J=5.2,1.8,0.9Hz,Ph-H,1H),5.55(s,=CH-,1H),4.57(s,Ph-CH2-N,2H),3.12(s,-CH3,3H). 13 C NMR (101MHz, CDCl3) δ189.17,173.76,136.79,135.11,130.50,128.60,127.11,125.16,93.38,57.47,40.04.

[0114] Embodiment 18

[0115] Synthesis of Compound I18 (R1 = 3-F-phenyl; R2 = -CH3)

[0116] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a brown solid with a yield of 76.9%. mp = 70.9-72.7°C. 1 H NMR (400MHz, CDCl3) δ7.40-7.34(m,Ph-H,1H),7.06-7.00(m,Ph-H,2H),6.93(dt,J= 9.4,2.1Hz,Ph-H,1H),5.55(s,=CH-,1H),4.59(s,Ph-CH2-N,2H),3.13(s,-CH3,3H). 13 C NMR (101MHz, CDCl3) δ189.16,164.42,161.95,137.30,137.23,130.90,130.82,122.63, 122.60,115.46,115.25,114.08,113.86,93.34,57.52,57.50,40.04.HRMS(ESI+):calcd for C 11 H 11 FNOS2(M+H) + 256.0260,found,256.0261.

[0117] Embodiment 19

[0118] Synthesis of compound I19 (R1 = 4-F-phenyl; R2 = -CH3)

[0119] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a yellow solid with a yield of 80.7%. mp = 56.6-57.8°C. 1 H NMR (400MHz, CDCl3) δ7.19 (dd, J = 8.4, 5.2Hz, Ph-H, 2H), 7.06 (t, J = 8.6Hz, Ph-H, 2H), 5.54 (s, = CH-, 1H), 4.55 (s, Ph-CH2-N, 2H), 3.07 (s, -CH3, 3H). 13 CNMR(101MHz, CDCl3)δ189.35,163.94,161.48,130.47,129.05,128.97,116.36,116.15,93.32,57.40,39.84.HRMS(ESI+):calcd for C 11 H 11 FNOS2(M+H) + 256.0259,found,256.0261.

[0120] Embodiment 20

[0121] Synthesis of compound I20 (R1 = 3-OCH3-phenyl; R2 = -CH3)

[0122] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a light yellow powder with a yield of 90.9%. mp = 106.3-107.8℃. 1 H NMR (400MHz, CDCl3) δ7.28 (d, J=7.9Hz, Ph-H, 1H), 6.85 (dd, J=8.3, 2.5Hz, Ph-H, 1H), 6.81-6.77 (m, Ph-H, 1H), 6.73(t,J=2.1Hz,Ph-H,1H),5.55(s,=CH-,1H),4.55(s,Ph-CH2-N,2H),3.80(s,-OCH3,3H),3.09(s,-CH3,3H). 13 C NMR(101MHz, CDCl3)δ189.40,173.94,160.28,136.30,130.38,119.33,113.35,113.13,93.25,58.04,55.43,40.02.HRMS(ESI+):calcd for C 12 H 14 FNO2S2(M+H) + 268.0458,found,268.0460.

[0123] Embodiment 21

[0124] Synthesis of Compound I21 (R1 = 4-OCH3-phenyl; R2 = -CH3)

[0125] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as a light yellow oil with a yield of 51.9%. 1 H NMR (400MHz, CDCl3) δ7.17 (d, J=6.6Hz, Ph-H, 1H), 7.13 (d, J=2.1Hz, Ph-H, 1H), 6.93-6.91 (m, Ph-H, 1H), 6. 84-6.81(m,Ph-H,1H),5.56(s,=CH-,1H),4.53(s,Ph-CH2-N-,2H),3.83(s,-OCH3,3H),3.06(s,-CH3,3H). 13 C NMR(101MHz, CDCl3)δ189.32,159.68,158.38,128.99,128.68,126.49,114.51,114.21,92.93,57.52,55.38,55.29,39.56.HRMS(ESI+):calcd for C 12 H 14 FNO2S2(M+H) + 268.0457,found,268.0460.

[0126] Embodiment 22

[0127] Synthesis of compound I22 (R1=3,5-(OCH3)2-phenyl;R2=-CH3)

[0128] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a light yellow solid with a yield of 76.9%. mp = 140.4-140.8°C. 1 H NMR (400MHz, CDCl3) δ6.66 (dt, J=2.0, 0.9Hz, Ph-H, 2H), 6.41 (t, J=2.0Hz, Ph-H, 1H), 5.56(s,=CH-,1H),4.47(s,Ph-CH2-N,2H),3.81(s,Ph-OCH3,6H),3.15(s,-CH3,3H); 13C NMR (101MHz, CDCl3) δ189.50,162.23,161.30,161.30,135.42,108.98,108.51,108.51,100.68,56.17,56.17,55.59,40.65.

[0129] Embodiment 23

[0130] Synthesis of compound I23 (R1 = 3-F-phenyl; R2 = -CH2CH3)

[0131] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as a yellow oil with a yield of 83%. 1 H NMR (400MHz, CDCl3) δ7.37-7.31(m,Ph-H,1H),7.03-6.91(m,Ph-H,3H),5.52(s,=CH-,1 H),4.57(s,Ph-CH2-N,2H),3.48(q,J=7.1Hz,N-CH2-,2H),1.25(t,J=7.2Hz,-CH3,3H). 13 C NMR(101MHz, CDCl3)δ189.47,173.09,164.52,162.06,137.61,130.88,122.55,114.63,93.37,55.23,48.10,12.22.HRMS(ESI+):calcd for C 12 H 13 FNOS2(M+H) + 270.0421,found,270.0417.

[0132] Embodiment 24

[0133] Synthesis of compound I24 (R1 = 3-OCF3-phenyl; R2 = H)

[0134] The synthesis method is the same as that of Example 1, except that the substituents are different. The target compound is obtained as an orange-yellow solid with a yield of 76.9%. mp = 75.6-76.8°C. 1 H NMR (400MHz, CDCl3) δ7.42(d,J=7.9Hz,-NH,1H),7.25(s,Ph-H,1H),7.24(s,Ph-H,1H),7.19( d,J=8.3Hz,Ph-H,1H),7.16(s,Ph-H,1H),5.58(s,=CH-,1H),4.44(d,J=4.2Hz,Ph-CH2-N,2H). 13CNMR (101MHz, CDCl3) δ190.40,173.29,149.81,138.13,130.66,125.84,121.76,120.80,120.08,94.30,49.88.

[0135] Embodiment 25

[0136] Synthesis of compound I25 (R1 = thiophenyl; R2 = -CH3)

[0137] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as a beige white solid with a yield of 90.6%. mp = 58.5-59.0°C. 1 H NMR (400MHz, CDCl3) δ7.29 (d, J=4.8Hz, thiophenyl-H, 1H), 7.01 (s, thiophenyl-H, 1H), 7.00-6. 97(m,thiophenyl-H,1H),5.58(s,=CH-,1H),4.71(s,thiophenyl-CH2-N,2H),3.10(s,-CH3,3H). 13 CNMR (101MHz, CDCl3) δ189.42,173.36,136.90,127.31,127.26,126.38,93.66,53.00,39.53.

[0138] Embodiment 26

[0139] Synthesis of Compound I26 (R1 = 2-chlorothiazoly; R2 = -CH3)

[0140] The synthesis method is the same as that of Example 1, except that the substituents are different, and the target compound is obtained as a light yellow solid with a yield of 73%. mp = 89.0-92.8°C. 1 H NMR (400MHz, CDCl3) δ7.46(s,2-chlorothiazoly-H,1H),5.54(s,=CH-,1H),4.65(d,J=1.2Hz,Ph-CH2-N,2H),3.08(s,-CH3,3H). 13 C NMR (101MHz, CDCl3) δ189.23,172.98,153.02,140.88,133.97,94.22,50.49,39.50.

[0141] Application Example 1 Antibacterial Activity Test of Compounds

[0142] The antibacterial activity of the target compounds against rice blast fungus was evaluated by the mycelial growth rate method. 0.9 g of each test compound was dissolved in 10 mL of DMF and diluted with 1‰ Tween-80 water to a solution with a concentration of 900 mg / mL. 5 mL of the resulting solution was added to 45 mL of sterile molten PDA to obtain the final test concentration (100 ppm). Then the PDA was poured into sterile culture dishes, 15 mL per dish. For the blank control, 10 mL of DMF was added to 10 mL of 1‰ Tween-80 water sterile aqueous solution. The mycelial disk cut from the subcultured PDA culture dish was inoculated in the PDA medium. The inoculated PDA culture dish was grown at a temperature of 25°C and a relative humidity of 60%. Calculation was performed according to the growth inhibition rate method. The commercially available fluopicolide (100 ppm) was used as the positive control reagent group, and the antibacterial test was carried out under the same conditions. Each treatment was tested three times. The antibacterial activity is shown in Table 1.

[0143] Table 1 Antibacterial activity of synthetic compound I

[0144]

[0145] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A dithiocyclopentenone derivative, characterized in that: The chemical structure is shown in formula (I): Wherein, R1 is selected from phenyl or substituted phenyl, pyridyl, thiazolyl, thienyl or piperazinyl; R2 is selected from H, -CH3 or -CH2CH3.

2. A method for preparing dithiocyclopentenone derivatives as claimed in claim 1, characterized in that: The following steps are involved: Will Anhydrous potassium carbonate and tetrahydrofuran are stirred in an ice-water bath, and then dichloro-1,2-dithiocyclopentenone is added and reacted at room temperature to obtain an intermediate; The intermediate is dissolved in acetonitrile, and iodotrimethylsilane is added. The reaction is carried out under nitrogen and room temperature. The reaction is stopped after the raw materials react completely. Saturated sodium bicarbonate solution and dichloromethane are continuously added dropwise to the reaction product for extraction. The organic phases are combined, and finally back-extracted once with sodium thiosulfate, dried, concentrated under reduced pressure, and subjected to column chromatography to obtain dithiocyclopentenone derivatives.

3. The method for preparing dithiocyclopentenone derivatives according to claim 2, characterized in that: Said The molar ratio of anhydrous potassium carbonate and dichloro-1,2-dithiocyclopentenone is 1:2:2; Said The usage ratio of tetrahydrofuran is 1g:40mL.

4. The method for preparing dithiocyclopentenone derivatives according to claim 2, characterized in that: The molar ratio of the intermediate to iodotrimethylsilane is 1:4; The usage ratio of the intermediate and acetonitrile is 0.3 g:10 mL.

5. Use of the dithiocyclopentenone derivatives as claimed in claim 1 in controlling and eliminating pathogenic bacteria of plant diseases, characterized in that: The pathogen is a pathogenic fungus.

6. A fungicide, characterized in that: The invention comprises 1-95 wt % of the dithiocyclopentenone derivatives according to claim 1.

7. The fungicide according to claim 6, characterized in that The fungicide also includes a surfactant and a carrier that are acceptable in pesticides.

8. The fungicide according to claim 6 or 7, characterized in that The dosage form of the fungicide is a pesticide-acceptable water-dispersible powder, suspension, granule, dry suspension, emulsifiable concentrate, aqueous solution, oil, fumigant, aerosol or microcapsule.

9. Use of the fungicide according to any one of claims 6 to 8 in controlling and eliminating pathogenic bacteria of plant diseases, characterized in that: The pathogen is a pathogenic fungus.

10. A sterilization method, characterized in that: The fungicide according to any one of claims 6 to 8 is applied to seeds, plants, fruits or growing soil.

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