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WO2020034992A1 - Composé contenant une structure hétérocyclique fusionné, son procédé de préparation et ses utilisations, et fongicide - Google Patents

Composé contenant une structure hétérocyclique fusionné, son procédé de préparation et ses utilisations, et fongicide Download PDF

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Publication number
WO2020034992A1
WO2020034992A1 PCT/CN2019/100570 CN2019100570W WO2020034992A1 WO 2020034992 A1 WO2020034992 A1 WO 2020034992A1 CN 2019100570 W CN2019100570 W CN 2019100570W WO 2020034992 A1 WO2020034992 A1 WO 2020034992A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound
phytophthora
heterocyclic structure
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/100570
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English (en)
Chinese (zh)
Inventor
杨光富
李建龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central China Normal University
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Central China Normal University
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Filing date
Publication date
Application filed by Central China Normal University filed Critical Central China Normal University
Publication of WO2020034992A1 publication Critical patent/WO2020034992A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings

Definitions

  • the invention relates to the field of pesticide fungicides, in particular to a compound with a fused heterocyclic structure and a preparation method thereof, the application of the compound with a fused heterocyclic structure in preventing and controlling plant oomycetes, and the compound with a fused heterocyclic structure Application as a pesticide fungicide and a fungicide.
  • Oomycetes are one of the important pathogens that cause plant diseases. They have a wide range of parasites, are highly destructive, harmful, and develop rapidly. They can harm most major cash crops such as potatoes, tomatoes, peppers, grapes, tobacco, and peppers. Wait. At the same time, the diseases caused by it are also difficult to prevent and control, thus causing great losses to agricultural production.
  • the main plant pathogens of oomycetes are Phytophthora infestans, Phytophthora capsici, Pythium ultimum, Phytophthora litchi, and Phytophthora cucumber.
  • Phytophthora infestans is a typical pathogen, and the late potato blight caused by it has caused the famous Irish famine in history.
  • Other plant pathogens can also cause severe disease occurrence.
  • Phytophthora capsici can easily cause diseases of pepper, tomato, eggplant and melons, and cucumber downy mildew caused by downy mildew of cucumbers.
  • the object of the present invention is to provide a new compound with a condensed heterocyclic structure to achieve a good effect of controlling oomycete diseases, especially to achieve a good effect of controlling ooge disease at low concentrations.
  • the present invention provides a compound having a fused heterocyclic structure or an agrochemically acceptable salt, hydrate, and solvate thereof, the compound having formula (1), formula (2), or The structure shown in formula (3),
  • the present invention provides the use of the fused heterocyclic structure-containing compound or the agrochemically acceptable salts, hydrates, and solvates thereof described in the first aspect in controlling plant oomycete diseases.
  • the present invention provides the use of the fused heterocyclic structure-containing compound or the agrochemically acceptable salts, hydrates, and solvates of the first aspect as pesticide fungicides.
  • the present invention provides a fungicide, which is composed of an active ingredient and an excipient, and the active ingredient includes the compound having a thick heterocyclic structure according to the first aspect of the present invention or an agrochemically acceptable compound thereof. At least one of a salt, a hydrate, and a solvate.
  • the compound containing a fused heterocyclic structure or the agrochemically acceptable salts, hydrates and solvates thereof provided by the present invention can effectively control plant oomycete diseases.
  • the experiment of the present invention shows that the compound of the present invention has excellent control effect on plant diseases caused by various oomycete pathogens such as cucumber downy mildew, Phytophthora capsici, Phytophthora infestans, and the like, and is obviously better than the conventional oocyst disease control agent Acylmorpholine has good market development prospects.
  • the first aspect of the present invention provides a compound having a fused heterocyclic structure or an agrochemically acceptable salt, hydrate and solvate thereof, the compound having the formula (1), the formula (2) Or the structure shown by formula (3),
  • the second aspect of the present invention provides a method for preparing the fused heterocyclic structure-containing compound according to the first aspect, which method comprises: under the conditions of a nucleophilic substitution reaction, converting formula (2-1) The compound shown is contacted with a compound represented by formula (11), formula (21) or formula (31),
  • the nucleophilic substitution reaction is performed in the presence of a basic reagent and in an anhydrous environment.
  • the alkaline reagent is at least one of sodium hydride, potassium carbonate, and cesium carbonate.
  • the basic conditions may be provided by a solvent such as tetrahydrofuran.
  • the contact reaction is performed in the presence of a solvent
  • the solvent is preferably at least one selected from the group consisting of dichloromethane, tetrahydrofuran, N, N-dimethylformamide, acetonitrile, and acetone.
  • the conditions of the contact reaction include: a reaction temperature of 0 to 60 ° C. and a reaction time of 2 to 48 h.
  • the compound represented by the formula (2-1) may be obtained from a commercial source, or may be synthesized by a method of the prior art according to a structural formula.
  • the present invention exemplarily provides a method for preparing the compound represented by the formula (2-1) in the examples, and those skilled in the art should not be construed as limiting the present invention.
  • the molar ratio of the compound represented by formula (2-1) to the compound represented by formula (11), formula (21) or formula (31) is 1: (1 To 3); more preferably 1: (1.2 to 2.4).
  • the product obtained after the contact reaction may also be subjected to post-treatment methods conventionally applied in the art to obtain a higher-purity product.
  • the post-treatment operation method includes: extraction , Washing, rotary evaporation, column chromatography, recrystallization and the like, the present invention is not particularly limited in this regard, as long as the aforementioned fused heterocyclic structure-containing compound of the present invention can be obtained.
  • the third aspect of the present invention provides the fused heterocyclic structure-containing compound or the agrochemically acceptable salts, hydrates, and solvates thereof according to the first aspect in the control of plant oomycete diseases. application.
  • the plant oomycete diseases include diseases caused by at least one of the pathogens, Phytophthora infestans, Phytophthora capsici, Phytophthora nicotianae, Phytophthora litchii, Phytophthora litchi, Phytophthora infestans and Downy mildew of cucumber .
  • the fourth aspect of the present invention provides the use of the fused heterocyclic structure-containing compound or the agrochemically acceptable salts, hydrates, and solvates thereof described in the first aspect as pesticide fungicides.
  • the fifth aspect of the present invention provides a fungicide, which is composed of an active ingredient and an excipient, and the active ingredient includes the compound having a condensed heterocyclic structure according to the first aspect, or an agricultural product thereof. At least one of chemically acceptable salts, hydrates, and solvates.
  • the content of the active ingredient is 1-99.9% by weight; more preferably, the content of the active ingredient is 5-95% by weight.
  • the dosage form of the bactericide is at least one selected from the group consisting of emulsifiable concentrate, suspending agent, wettable powder, powder, granule, aqueous preparation, poison bait, mother liquor and mother powder.
  • the auxiliary materials may be various auxiliary materials conventionally used in the art, and may be, for example, surfactants, solvents, and the like.
  • This example is used to illustrate a method for preparing a compound represented by formula (2-1).
  • This example is for explaining a method for preparing a compound represented by formula (1).
  • This example is for explaining a method for preparing a compound represented by formula (2).
  • This example is for explaining a method for preparing a compound represented by formula (3).
  • Test example 1 In vivo activity to inhibit downy mildew of cucumber (potted test)
  • test and investigation methods refer to the SOP-SC-1098 cucumber downy mildew potted method in the “Fungicide Volume of Standard Operating Practices for Pesticide Biological Activity Test” prepared by Kang Zhuo and Gu Baogen.
  • the compound of the present invention has a good control effect on cucumber downy mildew, and the control effect is 100% at four dosage concentrations of 20 mg / L to 0.625 mg / L.
  • Ethyl ketone is equivalent, especially the compound of formula (1).
  • the concentration is 0.208 mg / L
  • the control effect on cucumber downy mildew is still 100%.
  • the activities of the compounds of formula (1), formula (2) and formula (3) are better than those of the commercial fungicides dimethomorph and indoxacon.
  • Test Example 2 In Vitro Activity to Inhibit the Growth of Mycelium of Phytophthora capsici
  • the test method uses the microplate method to determine the biological activity in the pharmacy.
  • test agent was prepared into a 2,000 mg / L mother liquor with dimethyl sulfoxide, and then diluted to a concentration of 0.1 mg / L with sterile water, and stored at 4 ° C for use.
  • the compound of the present invention has a good inhibitory effect on the mycelial growth of Phytophthora capsici.
  • the inhibition rate is more than 90%, which is equivalent to that of the control agent fluorothiazolyl pyridone.
  • the compound of the present invention inhibits the mycelial growth of Phytophthora capsici by more than 90%, which is better than fluorothiazolyl ethyl ketone, formula (2), formula (3)
  • the compound shown is equivalent to fluorothiazolyl ketone, a control agent. .
  • the group arrangement is arranged in random blocks, each area is about 15m 2 , and each process is repeated twice.
  • the stem and leaf spray method is used to spray. Each time, the blank control is first sprayed, and then the same drug is sprayed according to the first low concentration and then high concentration. The sprayer is cleaned 3 times in different drug treatment rooms, and then sprayed to each community. Spray evenly. The test was started when the cucumber plants reached the 10-leaf stage and grew well. Six days after the first application, a second application was carried out for a total of two applications.
  • the number of disease spots in the entire plant is 11 to 20, and the disease spots are obviously spread, with occasional patches of disease spots;
  • the number of disease spots in the entire plant is about 20, the disease spots are obviously spread, and the disease spots are obviously continuous.
  • Table 3 show that the compound represented by formula (1) has a better control effect on cucumber downy mildew; when the test dose is above 12.5 mg / L, its control effect can reach more than 80%, and the control agent fluorothiazolyl ethyl Compared with ketones, at the same test dose (12.5mg / L, 25mg / L), the control effect is better; the control agent dimethomorph is less effective against cucumber downy mildew.
  • the compound represented by formula (1) is Both test doses were significantly better than dimethomorph.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention se rapporte au domaine des fongicides agricoles. L'invention concerne un composé contenant une structure hétérocyclique fusionné, son procédé de préparation et ses utilisations, et un fongicide. Le composé contenant une structure hétérocyclique fusionné a la structure représentée par la formule (1), la formule (2), ou la formule (3). Le composé selon la présente invention fournit d'excellents effets de lutte contre des maladies de plantes provoquées par divers pathogènes oomycètes tels que Phytophthora infestans, Phytophthora capsica, Pythium ultimum, Phytophthora nicotianae, Phytophthora litchi et Pseudoperonospora cubensis, est évidemment meilleur que l'agent diméthomorphe classique de lutte contre les oomycètes, et présente de grandes perspectives de développement de marché.
PCT/CN2019/100570 2018-08-14 2019-08-14 Composé contenant une structure hétérocyclique fusionné, son procédé de préparation et ses utilisations, et fongicide Ceased WO2020034992A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810924286 2018-08-14
CN201810924286.0 2018-08-14

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WO2020034992A1 true WO2020034992A1 (fr) 2020-02-20

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN111848612A (zh) * 2019-07-31 2020-10-30 华中师范大学 含稠杂环结构的化合物及其制备方法和应用以及杀菌剂
CN114989273A (zh) * 2022-06-29 2022-09-02 华南农业大学 基因PlMYB1R及其在防治荔枝霜疫霉病中的应用
CN119020316A (zh) * 2024-08-23 2024-11-26 华南农业大学 基因PlCaMK1及其在防治荔枝霜疫霉病中的应用

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CN113185509A (zh) * 2020-04-17 2021-07-30 华中师范大学 一种含吲哚环结构的化合物及其制备方法和应用、一种杀菌剂
CN118063453B (zh) * 2024-02-21 2025-02-07 南京吉星生物技术开发有限公司 苯并咪唑衍生物及其制备方法和应用、农用杀菌剂

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CN103180317A (zh) * 2010-08-25 2013-06-26 拜耳知识产权有限责任公司 作为杀菌剂的杂芳基哌啶和杂芳基哌嗪衍生物
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111848612A (zh) * 2019-07-31 2020-10-30 华中师范大学 含稠杂环结构的化合物及其制备方法和应用以及杀菌剂
CN111848612B (zh) * 2019-07-31 2021-09-14 华中师范大学 含稠杂环结构的化合物及其制备方法和应用以及杀菌剂
CN114989273A (zh) * 2022-06-29 2022-09-02 华南农业大学 基因PlMYB1R及其在防治荔枝霜疫霉病中的应用
CN119020316A (zh) * 2024-08-23 2024-11-26 华南农业大学 基因PlCaMK1及其在防治荔枝霜疫霉病中的应用
CN119020316B (zh) * 2024-08-23 2025-11-25 华南农业大学 基因PlCaMK1及其在防治荔枝霜疫霉病中的应用

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CN110818708B (zh) 2022-04-01

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