WO2016055029A1 - Use of eight-membered oxygen-bridge heterocyclic compound as insecticide synergist - Google Patents

Abstract

The present invention involves the use of an eight-membered oxygen-bridge heterocyclic compound as an insecticide synergist, and specifically discloses the use of a compound having the structure shown in formula (1) as an insecticide synergist, said formula being set forth in the description. The compound of the present invention is able at low concentrations noticeably to decrease the LD₅₀ or LC₅₀ of an insecticide, while having a strong enhancement effect in the prevention of such pests as planthoppers, whitefly, Aphis gossypii, Periplaneta americana, and houseflies.

Description

Use of octagonal oxygen bridge heterocyclic compound as insecticide synergist Technical field

The invention belongs to the field of pesticides. In particular, the present invention relates to a novel use of an eight-membered oxygen bridge heterocyclic compound as a neonicotinoid insecticide synergist.

Background technique

Most of the insecticides currently developed and utilized act on the nervous system of insects, such as ion channels, neurotransmitter receptors, enzymes that play an important role in the nervous system, etc., which act on insect nicotinic acetylcholine receptors (nAChRs). Neurotoxic agents have been the focus of research and development in recent years. The neonicotinoid insecticide represented by imidacloprid is the most intensively developed and utilized insecticide for insect nAChRs. Its mechanism of action is selective action on nAChRs in the insect central nervous system, destroying insects. The normal conduction of the central nervous system, making it extremely excited, gradually paralyzed until death, has high selectivity, high efficiency, low toxicity, strong systemicity, and low toxicity to mammals, good environmental compatibility, in agriculture Pest and hygienic pest control are widely used. Since the successful development of the first neonicotinoid insecticide imidacloprid in the early 1990s, there have been thiacloprid, acetamiprid, acetamiprid, thiamethoxam, clothianidin, dinotefuran, etc. A variety of varieties came out. However, the long-term, high-volume use of single-type insecticides has led to serious drug resistance problems, requiring the development of new agents or enhancing their activity through insecticide synergists. The new pesticides have a long cycle of creation and huge investment. In contrast, synergists have the advantages of less investment and quick results.

Insecticide synergists are a class of chemicals that have little or no insecticidal activity against insects, but which are added to an insecticide to greatly enhance the insecticidal efficacy of the insecticide. As early as the beginning of the Second World War, the US military began to use sesame oil as a synergist to make a concentrated preparation containing 5% to 20% of sesamin, which was incorporated into an aerosol or propellant of pyrethrin insecticide. The sesamin enhances the activity of the pyrethrin and enhances the activity of the natural pyrethrin. Since then, countries around the world have successively researched and developed piperine, synergistic esters, synergistic sulfones, synergistic rings, synergistic efficiencies, synergistic granules, synergistic aldehydes, synergistic ethers, synergistic amines, synergistic phosphorus, octachlor A series of products such as dipropyl ether, AI-1 type, multifunctional ninety-four O and S-855 plant source synergist. The synergist mainly improves the insecticidal effect of the insecticide by changing the physical properties of the insecticide, changing the penetrating ability of the insecticide on the epidermis, and inhibiting the metabolic detoxification enzyme activity of the pest.

Neonicotinoid insecticides are selective agonists of insect nicotinic acetylcholine receptors (nAChRs), and due to their mechanism of action, existing synergists are difficult to synergize. Specific potentiators for such insecticides have not been reported in the literature.

Summary of the invention

The object of the present invention is to provide a new use of an eight-membered oxygen bridge heterocyclic compound as a synergist for insecticides, which is compounded with a neonicotinoid insecticide, which can significantly increase the insecticidal action and reduce the insecticidal effect. Prevention and control of agricultural pests and sanitary pests cost.

In a first aspect of the invention, there is provided the use of an eight-membered oxygen bridged heterocyclic compound as a pesticide synergist, the octa- oxy bridged heterocyclic compound being a compound of the formula (1), Or an optical isomer, a cis-trans isomer thereof, or a pesticide-acceptable salt thereof;

In the formula:

R ₁ is H, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, nitrogen, oxygen and/or sulfur a five- or six-membered heterocyclic group, a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted phenyl group; said substitution means selected from the group consisting of Substituted by one or more substituents: halogen, C _1-4 haloalkyl or C _1-4 chloroalkoxy;

R ₂ , R ₃ are each independently H, C _1-6 alkyl, allyl, benzyl, C _1-4 alkoxy-C _1-4 alkyl, C _1-4 alkoxy-carbonyl, Phenoxycarbonyl, C _2-6 alkynyl-carbonyl, C _2-3 alkenyl-carbonyl, C _3-6 cycloalkyl-carbonyl, benzoyl or by one or more selected from halogen atoms, C _1-4 a benzoyl group substituted with a substituent of an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 alkyl-carbonyl group, a furancarbonyl group, an N,N-dimethylcarbonyl group, or an R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -;

R ₄ , R ₅ , R ₆ are each independently H, saturated or unsaturated C _1-4 alkyl, halogen, C _1-8 saturated or unsaturated alkoxy, halogenated C _1-4 saturated or unsaturated Alkoxy, C _1-4 alkyl-carbonyl, C _1-8 alkyl-ester, C _1-4 alkyl-sulfonate, phenyl or benzyl;

Y is C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, benzyl, nitro, cyano, trifluoromethyl Base, trifluoroacetyl or trifluoromethanesulfonyl.

In another preferred embodiment, R _{1 is} selected from the group consisting of pyridyl, thiazolyl, tetrahydrofuranyl, phenyl, C _1-6 alkyl or C _1-6 alkoxy.

In another preferred embodiment, R ₂ and R ₃ are each independently H or C _1-2 alkyl, or R ₂ and R ₃ together form -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -.

In another preferred embodiment, R ₄ , R ₅ , and R ₆ are each independently H.

In another preferred embodiment, Y is nitro, cyano, trifluoromethyl, trifluoroacetyl or trifluoromethanesulfonyl.

In another preferred embodiment, in the compound, any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Y is respectively corresponding to each of the specific compounds described in the respective examples or Table 7. Group.

In another preferred embodiment, the insecticide is a neonicotinoid insecticide.

In another preferred embodiment, the insecticide is selected from the group consisting of imidacloprid, acetamiprid, thiacloprid, clothianidin, nitenpyram, chlorothiazol, thiamethoxam, dinotefuran.

In another preferred embodiment, the effective concentration of the octagonal oxygen bridge heterocyclic compound is from 0.5 to 2500 mg/L; and / Or the weight ratio of the octagonal oxygen bridge heterocyclic compound to the neonicotinoid insecticide is 1:50 to 100:1.

In another preferred embodiment, the effective concentration of the octagonal oxygen bridge heterocyclic compound is from 0.5 to 1000 mg/L, preferably from 1 to 500 mg/L, more preferably from 10 to 200 mg/L.

In another preferred embodiment, the weight ratio of the octa-oxy bridged heterocyclic compound to the neonicotinoid insecticide is 1:10 to 50:1.

According to a second aspect of the present invention, there is provided an eight-membered oxygen bridged heterocyclic compound which is a compound represented by the formula (1), or an optical isomer thereof, a cis-trans isomer thereof , or a pesticide acceptable salt thereof;

In the formula:

When R ₁ is H, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy,

R ₂ , R ₃ are each independently H, C _1-6 alkyl, allyl, benzyl, C _1-4 alkoxy-C _1-4 alkyl, C _1-4 alkoxy-carbonyl, Phenoxycarbonyl, C _2-6 alkynyl-carbonyl, C _2-3 alkenyl-carbonyl, C _3-6 cycloalkyl-carbonyl, benzoyl or by one or more selected from halogen atoms, C _1-4 a benzoyl group substituted with a substituent of an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 alkyl-carbonyl group, a furancarbonyl group, an N,N-dimethylcarbonyl group, or an R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -;

R ₄ , R ₅ , R ₆ are each independently H, saturated or unsaturated C _1-4 alkyl, halogen, C _1-8 saturated or unsaturated alkoxy, halogenated C _1-4 saturated or unsaturated Alkoxy, C _1-4 alkyl-carbonyl, C _1-8 alkyl-ester, C _1-4 alkyl-sulfonate, phenyl or benzyl;

Y is C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, benzyl, nitro, cyano, trifluoromethyl Base, trifluoroacetyl or trifluoromethanesulfonyl;

or

When R ₁ is a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted benzene group The substituent refers to being substituted with one or more substituents selected from the group consisting of halogen, C _1-4 haloalkyl or C _1-4 chloroalkoxy;

R ₂ , R ₃ are each independently H, C _1-6 alkyl, allyl, benzyl, C _1-4 alkoxy-C _1-4 alkyl, C _1-4 alkoxy-carbonyl, Phenoxycarbonyl, C _2-6 alkynyl-carbonyl, C _2-3 alkenyl-carbonyl, C _3-6 cycloalkyl-carbonyl, benzoyl or by one or more selected from halogen atoms, C _1-4 a benzoyl group substituted with a substituent of an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 alkyl-carbonyl group, a furancarbonyl group, an N,N-dimethylcarbonyl group, or an R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -;

R ₄ , R ₅ , R ₆ are each independently H, saturated or unsaturated C _1-4 alkyl, halogen, C _1-8 saturated or unsaturated alkoxy, halogenated C _1-4 saturated or unsaturated Alkoxy, C _1-4 alkyl-carbonyl, C _1-8 alkyl-ester, C _1-4 alkyl-sulfonate, phenyl or benzyl;

Y is C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy;

or

When R ₁ is phenyl or chlorophenyl, R ₂ and R ₃ together form -CH ₂ -CH ₂ -, and R ₄ , R ₅ and R ₆ are each independently H and Y is a nitro group.

In another preferred embodiment, R ₁ is H, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 fluoroalkyl, C _1-6 chloroalkyl, C _{1- 6} bromoalkyl.

In another preferred embodiment, R ₁ is methyl, ethyl, propyl, butyl, halomethyl, haloethyl, halopropyl, halobutyl.

In another preferred embodiment, the halo is fluoro or chloro.

In another preferred embodiment, in the compound, any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Y is a group corresponding to the specific compound described in each of the examples. .

In a third aspect of the present invention, there is provided an agricultural composition comprising the active ingredient (a): a compound represented by the formula (1), or an optical isomer thereof, a cis-trans isomer thereof, or a pesticide thereof The salt to be accepted; and the active ingredient (b): an insecticide; and the weight ratio of the active ingredient (a) to the active ingredient (b) is 1:100 to 100:1;

In the formula:

R ₁ is H, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, nitrogen, oxygen and/or sulfur a five- or six-membered heterocyclic group, a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted phenyl group; said substitution means selected from the group consisting of Substituted by one or more substituents: halogen, C _1-4 haloalkyl or C _1-4 chloroalkoxy;

R ₂ , R ₃ are each independently H, C _1-6 alkyl, allyl, benzyl, C _1-4 alkoxy-C _1-4 alkyl, C _1-4 alkoxy-carbonyl, Phenoxycarbonyl, C _2-6 alkynyl-carbonyl, C _2-3 alkenyl-carbonyl, C _3-6 cycloalkyl-carbonyl, benzoyl or by one or more selected from halogen atoms, C _1-4 a benzoyl group substituted with a substituent of an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 alkyl-carbonyl group, a furancarbonyl group, an N,N-dimethylcarbonyl group, or an R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -;

R ₄ , R ₅ , R ₆ are each independently H, saturated or unsaturated C _1-4 alkyl, halogen, C _1-8 saturated or unsaturated alkoxy, halogenated C _1-4 saturated or unsaturated Alkoxy, C _1-4 alkyl-carbonyl, C _1-8 alkyl-ester, C _1-4 alkyl-sulfonate, phenyl or benzyl;

Y is C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, benzyl, nitro, cyano, trifluoromethyl Base, trifluoroacetyl or trifluoromethanesulfonyl.

In another preferred embodiment, the weight ratio of the active ingredient (a) to the active ingredient (b) is from 1:50 to 100:1; preferably, from 1:50 to 50:1; more preferably, 1: 20 to 50:1; more preferably, 1:20 to 20:1; more preferably 1:10 to 10:1; more preferably 1:5 to 5:1; more preferably, 1:1~2:1.

In another preferred embodiment, R _{1 is} selected from the group consisting of pyridyl, thiazolyl, tetrahydrofuranyl, phenyl, C _1-6 alkyl or C _1-6 alkoxy.

In another preferred embodiment, R ₂ and R ₃ are each independently H or C _1-2 alkyl, or R ₂ and R ₃ together form -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -.

In another preferred embodiment, R ₄ , R ₅ , and R ₆ are each independently H.

In another preferred embodiment, Y is nitro, cyano, trifluoromethyl, trifluoroacetyl or trifluoromethanesulfonyl.

In another preferred embodiment, in the compound, any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Y is respectively corresponding to each of the specific compounds described in the respective examples or Table 7. Group.

In another preferred embodiment, the insecticide is a neonicotinoid insecticide.

In another preferred embodiment, the insecticide is selected from the group consisting of imidacloprid, acetamiprid, thiacloprid, clothianidin, nitenpyram, chlorothiazol, thiamethoxam, dinotefuran.

In another preferred embodiment, the agricultural composition is a solution, an emulsion, a suspension, a powder, a foaming agent, a paste, a granule, an aerosol, a natural and synthetic material impregnated with an active ingredient, and micro Capsules, coatings, formulations for use with combustion devices, ULV Cold mist or Warm mist formulations.

In a fourth aspect of the invention, there is provided the use of the agricultural composition according to the third aspect of the invention or the compound according to the second aspect of the invention for killing or preventing agricultural pests, sanitary pests and pests which are harmful to animal health; Or used as a pesticide composition for killing or preventing agricultural pests, sanitary pests, and pests that are harmful to animal health.

In another preferred embodiment, the agricultural composition is used to kill or prevent a pest selected from the group consisting of Hemiptera, Orthoptera, Acarina or Diptera.

In another preferred embodiment, the Hemiptera insects include: brown planthopper, Laodelphax striatellus, whitebacked planthopper, whitefly, cotton aphid, peach aphid, spider mites.

In another preferred embodiment, the insects of the order include: American cockroach, German cockroach.

In another preferred embodiment, the Orthoptera insects include: East Asian migratory locust and desert locust.

In another preferred embodiment, the Diptera insects include: Musca domestica, Aedes aegypti, Musca domestica, Culex pipiens, Anopheles sinensis.

In another preferred embodiment, the compound has an effective concentration of from 0.5 to 2500 mg/L.

In another preferred embodiment, the compound has an effective concentration of 0.5 to 1000 mg/L, preferably 1 to 500 mg/L, more preferably 10 to 200 mg/L.

In another aspect, the present invention provides a pesticidal and/or pest control method, the method comprising the steps of: adding the agricultural composition of the third aspect of the invention to a plant body suffering from or possibly suffering from pests, surrounding thereof In the soil or in the environment.

In another preferred embodiment, the weight ratio of the active ingredient (a) to the active ingredient (b) in the agricultural composition is 1:100 to 100:1; preferably, 1:50 to 100:1; Preferably, it is 1:50 to 50:1; more preferably 1:20 to 50:1; more preferably 1:20 to 20:1; more preferably 1:10 to 10: 1; more preferably, it is 1:5 to 5:1; more preferably, it is 1:1 to 2:1.

In another preferred embodiment, the active ingredient (a) has an effective concentration of from 0.5 to 2500 mg/L.

In another preferred embodiment, the active ingredient (a) has an effective concentration of 0.5 to 1000 mg/L, preferably 1 to 500 mg/L, more preferably 10 to 200 mg/L.

It is to be understood that within the scope of the present invention, the various technical features of the present invention and the various technical features specifically described hereinafter (as in the embodiments) may be combined with each other to constitute a new or preferred technical solution. Due to space limitations, we will not repeat them here.

DRAWINGS

Figure 1 shows the synergistic effect of compound 8 on acetamiprid, acetamiprid, thiacloprid, and clothianidin in American cockroaches and brown planthopper. Among them, the A picture is the result of the American cockroach, and the B picture is the result of the brown planthopper.

Figure 2 shows the effective concentration of Compound 8 on imidacloprid in the brown planthopper.

Detailed ways

The present inventors have found for the first time that the octagonal oxygen bridge heterocyclic compound represented by the formula (1) has a synergistic effect on insecticides, and in particular, synergistic effect on neonicotinoid insecticides. The above oxygen bridge heterocyclic compound is compounded with a neonicotinoid insecticide to significantly increase its insecticidal action. On the basis of this, the present invention has been completed.

Pesticide composition

The active ingredient of the present invention can be prepared into a pesticidal composition in a conventional manner. The term "active ingredient of the present invention" includes the active ingredient (a): a compound represented by the formula (1), or an optical isomer thereof, a cis-trans isomer thereof, or a pharmaceutically acceptable salt thereof, and an activity thereof. Ingredient (b): Insecticide (including any commercially available insecticide). The active ingredient (a) itself has low or no insecticidal activity at low concentrations (eg 4.5 ng/worm), but has a significant synergistic effect on the active ingredient (b), which can significantly increase the active ingredient (b) Insecticidal activity.

Preferably, in the agricultural composition, the weight ratio of the active ingredient (a) to the active ingredient (b) is from 1:100 to 100:1; preferably, from 1:50 to 100:1; preferably, It is 1:50 to 50:1; more preferably 1:20 to 50:1; more preferably 1:20 to 20:1; more preferably 1:10 to 10:1; more preferably The ground is 1:5 to 5:1; more preferably, it is 1:1 to 2:1.

The preparation method of the compound represented by the above formula (1), its optical isomer, cis-trans isomer or agrochemically acceptable salt is referred to the patent CN200810207355.2.

The term "agrochemically acceptable salt" means that the anion of the salt is known and acceptable in forming the pharmaceutically acceptable salt of the pesticide. The salt is preferably water soluble. Suitable acid addition salts formed from the compounds of formula (1) include salts formed with inorganic acids, such as hydrochlorides, phosphates, sulfates, nitrates; and salts formed from organic acids, such as acetates, Benzoate.

The pesticide composition of the invention can be used for controlling and eliminating a wide range of agricultural and forestry plant pests, storing pests of cereals, and public Hygienic pests and pests that endanger animal health. In the present specification, examples of pests include, but are not limited to, Coleoptera: Sitophilus zeamais, Tribolium castaneum, Henosepilachna vigintioctomaculata, and 18-spot ladybug (Henosepilachna sparsa) ), Agriotes fuscicollis, Anomala cupripes, Popillia quadriguttata, Monolepta hieroglyphica, Monochamus alternatus, Echinocnemus Squameus), Basiprionota bisignata, Anoplophora chinensis, Apripona germari, Scolytus schevy, or Agriotes fuscicollis; Hemiptera : Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis gossydii, radish (Lipaphis erysimi pseudobrassicae), Stephanitis nashi, or Bemisia tabaci; Insects: Blattella germanica, or Periplaneta american; Orthoptera: Gryllotalpa africana, or Locus migratoria; Isoptera: Invasion Ant (Solenopsis invicta), or domestic termite (Coptotermes formosanus); Diptera: Musca domestica, Aedes aegypti, Delia platura, Culex sp., or Anopheles sinensis. Animals that are harmful to animal health include Boophilus microplus, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, and shellfish. Moniezia blanchard, Ostertagiaspp., Protozoa Trypanosoma enansi, Babesia bigemina, etc.

The compounds of the present invention have particular effects on pests such as sucking and sucking mouthparts, such as brown planthopper, Laodelphax striatellus, B. tabaci, cotton aphid, American cockroach, and housefly.

The active ingredient of the present invention can be formulated into conventional preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granules; aerosols, natural and synthetic materials impregnated with active ingredients, Microcapsules in polymers, coatings for seeds, and preparations for use with combustion devices, such as smoked cartridges, smoked cans and smokers, as well as ULV cold mist and hot fog (Warm mist) preparation.

These preparations can be produced by known methods, for example, by mixing the active ingredient with an extender, which is a liquid or liquefied gas or solid diluent or carrier, and optionally a surfactant, an emulsifier and/or A dispersant and/or a foam former. For example, when water is used as an extender, an organic solvent can also be used as an auxiliary.

Basically suitable when using a liquid solvent as a diluent or carrier, such as: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or Dichloromethane; aliphatic hydrocarbons such as cyclohexane or paraffin, such as mineral oil fractions; alcohols such as ethanol or ethylene glycol and their ethers and lipids; ketones such as acetone, methyl ethyl ketone, methyl isobutyl Ketone or cyclohexanone; or less common polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. The diluent or carrier of the liquefied gas refers to a liquid which will become a gas at normal temperature and pressure, for example Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.

The solid carrier may be a naturally ground mineral such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates. . The solid carrier for the granules is a ground and graded natural stone, such as calcite, marble, pumice, sepiolite and dolomite, as well as inorganic and organic coarse powder granules, and organic materials such as sawdust, coconut shell, Corn cobs and granules of tobacco stems.

Emulsified columns of nonionic and anionic agents can be used as emulsifiers and/or foam formers. For example, polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and white Protein hydrolysate. Dispersing agents include, for example, lignin sulfite waste liquid and methyl cellulose.

Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions such as acacia, polyvinyl alcohol and polyvinyl acetate may be employed in the formulation. Colorants such as inorganic dyes such as iron oxide, oxidized diamonds and Prussian blue; organic dyes such as organic dyes such as azo dyes or metal phthalocyanine dyes; and trace nutrients such as iron, lanthanum, boron, copper may be used. , cobalt, aluminum and zinc salts, etc.

The main advantages of the invention include:

The present invention provides a novel use of a compound represented by the formula (1) (see the patent CN200810207355.2 for the preparation method) as a synergist for insecticides. The compound can greatly enhance the efficacy of existing insecticides (especially neonicotinoid insecticides), reduce the use of pesticides, and reduce the cost of controlling various agricultural pests and sanitary pests. Resistance control plays an important role.

The invention is further illustrated below in conjunction with specific implementations. It is to be understood that the examples are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually in accordance with conventional conditions or according to the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

Preparation example

Example 1: 1-(4-Chlorophenyl)-10-nitro-1,2,3,5,6,7,8,9-octahydro-5,9-epoxyimidazo[1,2 -a] Synthesis of azacyclotetracycline (Compound 9)

1.27 g (0.005 mol) of 1-(4-chlorophenyl)-2-(nitromethylene)imidazolidine, 30 ml of anhydrous acetonitrile, 3 ml of 25% aqueous solution of glutaraldehyde, and a catalytic amount of HCl in 50 ml In a round bottom flask. Stir at room temperature and TLC followed the reaction. After the end of the reaction, the solvent was removed, and the residue was purified by column chromatography to yield pale-yellow powdery product. Mp=174.7-175.4°C; ¹ H NMR (400Mz, DMSO-d ₆ ): δ 7.39 (s, 306H), 7.32 (s, 307H), 4.84 (s, 308H), 4.73 (s, 154H), 4.46 (s, 158H), 3.22 (s, 80H), 3.14 (s, 86H), 2.89 (s, 87H), 2.84 (s, 82H), 1.94 (t, J = 3.5 Hz, 30H), 1.93 (s, 148H), 1.77 (dd, J = 65.0, 60.0 Hz, 590H), 1.56 (d, J = 80.0 Hz, 257H), 1.46 (d, J = 1.6 Hz, 6H) ppm; ¹³ C NMR (100 Mz, DMSO- d ₆ ): δ 167.96, 136.07, 132.68, 129.50, 128.21, 80.05, 64.91, 54.33, 50.62, 47.77, 31.93, 31.54, 15.74 ppm; HRMS (EI+) calculated C ₁₆ H ₁₈ N ₃ O ₃ ³⁵ Cl (M ⁺ ), 335.7854; measured value, 335.7850. Calculated C ₁₆ H ₁₈ N ₃ O ₃ ³⁷ Cl (M ⁺ ), 337.1007; measured value, 337.1000.

Example 2: 1-(3-Fluoropropyl)-1,2,3,5,6,7,8,9-octahydro-5,9-epoxyimidazo[1,2-a]azacyclocycle Synthesis of octene-10-nitrile (Compound 10):

0.845 g (5.0 mmol) of 2-(1-(3-fluoropropyl)imidazolin-2-ylidene)acetonitrile and 3 ml of 25% aqueous solution of glutaraldehyde were added to 20 ml of acetonitrile, and a catalytic amount of concentrated hydrochloric acid was added thereto, and stirred at room temperature. After TLC was traced, after the reaction was completed, the solvent was removed, and the residue was purified by column chromatography to give a white powdery product. ^{1 H NMR (400MHz, DMSO-} d 6) δ4.94 (s, 8H), 5.95-2.81 (m, 74H), 3.23 (s, 4H), 3.10 (s, 8H), 3.41-2.81 (m, 36H ), 2.96 (d, J = 17.4 Hz, 14H), 2.80 (s, 4H), 1.93 (s, 6H), 1.83 (s, 9H), 1.73 (d, J = 4.0 Hz, 14H), 1.71 - 1.46 (m, 24H) ppm; ¹³ C NMR (100MHz, DMSO-d ₆ ): δ 151.48, 120.64, 80.76, 80.05, 65.24, 61.05, 52.63, 49.19, 47.77, 31.54, 30.45, 26.78, 15.74 ppm; HRMS (ES+) For C ₁₃ H ₁₉ FN ₃ O (M+H) ⁺ , found: 2521.467;

Example 3: 1-Benzyl-10-nitro-1,2,3,5,6,7,8,9-octahydro-5,9-epoxyimidazo[1,2-a]aza Synthesis of cyclooctane tetramine (compound 6)

1.10 g (0.005 mol) of 1-benzyl-2-(nitromethylene)imidazolidine, 30 ml of anhydrous acetonitrile, 3 ml of 25% aqueous solution of glutaraldehyde, and a catalytic amount of HCl in a 50 ml round bottom flask in. Stir at room temperature and TLC followed the reaction. After the completion of the reaction, the solvent was removed, and the residue was purified by column chromatography to yield a pale yellow powder. ^{mp = 154.7-155.4 ℃; 1 H NMR} (400Mz, DMSO-d 6): δ7.36 (s, 82H), 7.29 (d, J = 15.0Hz, 170H), 4.84 (s, 110H), 4.74 (s , 55H), 4.60 (s, 58H), 3.18 (s, 30H), 3.08 (s, 31H), 2.80 (d, J = 13.8 Hz, 85H), 1.94 (t, J = 3.5 Hz, 11H), 1.93 (s, 53H), 1.77 (dd, J = 65.0, 60.0 Hz, 211H), 1.56 (d, J = 80.0 Hz, 92H) ppm; ¹³ C NMR (100 Mz, DMSO-d ₆ ): δ 167.96, 137.34, 128.64 , 128.56, 127.89, 80.05, 64.91, 54.33, 50.62, 47.77, 31.93, 31.54, 15.74 ppm; HRMS (EI+) calculated C ₁₆ H ₁₉ N ₃ O ₃ (M ⁺ ), 301.1426; measured value, 301.1420.

Example 4: 1-(3-Chloropropyl)-10-nitro-1,2,3,5,6,7,8,9-octahydro-1H-5,9-epoxyimidazole [1, Synthesis of 2-a]azetidine (Compound 12)

1.025 g (5.0 mmol) of 1-(3-chloropropyl)-2-(nitromethylene)imidazole and 3 ml of 25% aqueous solution of glutaraldehyde were added to 20 ml of acetonitrile, and a catalytic amount of concentrated hydrochloric acid was added thereto, and stirred at room temperature. After TLC was traced, after the reaction was completed, the solvent was removed, and the residue was purified by column chromatography to give a yellow powdery product. ^{1 H NMR (400MHz, DMSO-} d 6) δ4.62 (s, 2H), 4.17 (s, 2H), 3.75 (s, 2H), 3.35 (s, 1H), 3.23 (s, 1H), 3.08 ( s, 2H), 3.01 (s, 1H), 2.85 (d, J = 13.1 Hz, 3H), 2.17 (s, 2H), 1.93 (s, 1H), 1.74 (d, J = 4.0 Hz, 3H), 1.66 (d, J = 16.0 Hz, 4H), 1.48 (s, 1 H) ppm; ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ 167.17, 80.05, 64.91, 52.63, 49.04, 47.77, 41.28, 31.93, 31.54, 28.02, 15.74 ppm; HRMS (ES+) C ₁₂ H ₁₉ ³⁵ ClN ₃ O ₃ (M+H) ⁺ , Calculated: 288.1070; found: 288.1060; C ₁₂ H ₁₉ ³⁷ ClN ₃ O ₃ (M+H ⁺ , calculated value: 290.1041; measured value: 290.1030.

Example 5: 1-Methyl-10-nitro-1,2,3,5,6,7,8,9-octahydro-5,9-epoxyimidazo[1,2-a]azacyclocycle Synthesis of octene (Compound 13):

0.645 g (5.0 mmol) of 2-(nitromethylene)imidazoline and 3 ml of 25% aqueous solution of glutaraldehyde were added to 20 ml of acetonitrile, and a catalytic amount of concentrated hydrochloric acid was added thereto, stirred at room temperature, followed by TLC, and after the reaction was completed, The solvent was separated by column chromatography to give a yellow powdery product, yield 77%. ^{1 H NMR (400MHz, DMSO-} d 6) δ4.60 (s, 13H), 4.22 (s, 11H), 3.18 (s, 7H), 3.10 (s, 7H), 3.00 (s, 38H), 2.85 ( s, 11H), 2.81 (s, 9H), 1.93 (s, 6H), 1.74 (d, J = 5.0 Hz, 16H), 1.68 (s, 16H), 1.56 (d, J = 80.0 Hz, 24H), 1.46–1.29 (m, 3H) ppm; ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ 154.86, 80.04, 64.92, 50.99, 47.44, 36.61, 31.93, 31.54, 15.74 ppm; HRMS (ES+) C ₁₀ H ₁₅ N ₃ O ₃ (M+H) ⁺ , Calcd.: 226.1147; Found: 226.1141.

Synergistic embodiment

Example 6: Synergism of Compound 8

Test agent

Insecticides: imidacloprid, acetamiprid, thiacloprid, and clothianidin were purchased from Sigma-Aldrich, St. Louis, MO, USA;

Synergist: Compound 8:

The synthesis method is referred to the patent CN200810207355.2.

2. Bioassay

2.1 The bioassay method of Nilarpavata lugens and Laodelphax striatellus is a drip method.

The pesticide or the compound 8 is dissolved in acetone, respectively, and the mother liquor is prepared at a concentration of 1500 mg/L, and the prepared pesticide and the mother liquor of the compound 8 are mixed according to a series of ratios, and diluted with acetone to form a series. Concentration gradient. The 3rd instar nymph of the planthopper was anesthetized with CO _{2 for} 15 s, and then the drug solution was dripped on the front chest plate of the test insect using a micrometer. Thirty test insects were treated at each concentration, repeated 3 times, and acetone was used as a control. The treated test insects are connected to a feeding cup containing soilless cultivated rice seedlings, and cultured at a temperature of 27±1° C., a relative humidity of 70% to 80%, and a photoperiod of 16/8 h (L/D). The results were checked after 24 hours of treatment.

2.2 Periplaneta americana bioassay method is a spot method.

The pesticide or the compound 8 is dissolved in acetone, respectively, and the mother liquor is prepared at a concentration of 1500 mg/L, and the prepared pesticide and the mother liquor of the compound 8 are mixed according to a series of ratios, and diluted with acetone to form a series. Concentration gradient, the drug solution was dripped on the back of the male adult's abdomen with a micropipette, and acetone was used as a control. 30 test insects were treated at each concentration and repeated 3 times. The treated test insects are connected to the terrarium and provide sufficient food and water to be cultured at a temperature of 27±1°C, a relative humidity of 70%-80%, and a photoperiod of 16/8h (L/D). The results were checked after 24 hours.

2.3 Bemisia tabaci (Q type) bioassay method is the leaf dip method.

The pesticide or the compound 8 was separately dissolved in DMF, and each was prepared into a mother liquor having a concentration of 1500 mg/L, and the prepared insecticide and the mother liquor of the compound 8 were mixed in a series of ratios to obtain a mixed mother liquor. The prepared single-agent or mixed drug mother liquor was diluted with distilled water containing 0.1 Torr Triton X-100 to prepare a series concentration, and another set of the control was used to replace the single agent or the mixed drug mother liquor with DMF. The cabbage leaves were made into 22 mm diameter discs, completely immersed in a series of chemical solutions for 10 s, and the leaves were removed upwards and moved to a flat-bottomed test tube with 15 g/L agar. Each tube was connected to 30 healthy adults of the same size, sealed with gauze, and each treatment was repeated 3 times. The culture was carried out under the conditions of a temperature of 25 ± 1 ° C and a photoperiod of 14/10 h (L/D), and the results were examined after 24 hours of treatment.

2.4 Aphis gossypii was collected from cotton fields in Weifang, Shandong Province, and the bioassay method was impregnation.

The preparation method of the medicament was the same as that of the above-described leaf-leaching method, and 30 finless sputum was placed in a spherical filter of a 0.5 mm-diameter metal mesh, and the solution was immersed in the liquid for 10 s and taken out. The cotton aphid after the dipping was placed on a clean filter paper, and the excess liquid was aspirated and transferred to cotton seedlings, and each treatment was repeated 3 times. The culture was carried out under the conditions of a temperature of 25 ± 1 ° C and a photoperiod of 14/10 h (L/D), and the results were examined after 24 hours of treatment.

2.5 Musca domestica bioassay method is artificial feed addition method.

The pesticide or the compound 8 was separately dissolved in acetone, and each was prepared into a mother liquor having a concentration of 1500 mg/L, and the prepared insecticide and the mother liquor of the compound 8 were mixed in a series of ratios to obtain a mixed mother liquor. The prepared single-agent or mixed drug mother liquor was diluted with distilled water containing 0.1 Torr Triton X-100 to prepare a series concentration, and another set of the control was used with acetone instead of the single agent or the mixed drug mother liquor. Take 5g artificial diet, add 10mL diluted single dose or mixed drug evenly, and connect 20 2nd instar nymphs, each treatment is repeated 3 times. The culture was carried out under the conditions of a temperature of 25 ± 1 ° C and a photoperiod of 14/10 h (L/D), and the results were examined after 24 hours of treatment.

3. Data processing

The results of bioassay were processed by DPS v7.05 analysis software, and the virulence regression curve equation, LC ₅₀ , 95% confidence limit and correlation coefficient of the tested agents were calculated.

Relative virulence = [LD ₅₀ or LC _{50 of} (insecticide + synergist)] / [LD ₅₀ or LC _{50 of} insecticide]

= Synergy factor [LD ₅₀ of pesticides or LC _50] / [(+ insecticide synergist) or LD ₅₀ of LC _50)]

First, the synergistic effect of Compound 8 on imidacloprid was tested in brown planthopper, Laodelphax striatellus, B. tabaci, Aphis gossypii, American cockroach and Musca domestica. The results are shown in Table 1.

Table 1 Synergistic effect of compound 8 on imidacloprid in different insects

Note: a indicates the same unit

It can be seen from Table 1 that in a variety of agricultural pests and sanitary pests, low concentration of Compound 8 can significantly reduce the LD ₅₀ /LC _{50 of} imidacloprid, and has a strong synergistic effect.

In the brown planthopper, when the compound 8 with a concentration greater than 0.75 ng/worm was mixed with imidacloprid, the insecticidal activity of imidacloprid was significantly enhanced; when the concentration was 2.5 ng/worm, the synergistic effect peaked, and the synergistic multiple was 7.31 times.

In the American cockroach, when the compound 8 with a concentration greater than 1.75 μg/worm was mixed with imidacloprid, the insecticidal activity of imidacloprid was significantly enhanced; when the concentration was 3.75 μg/worm, the synergistic effect peaked and the synergistic multiple was 5.56 times.

Among the pests such as Laodelphax striatellus, B. tabaci, Aphis gossypii and Musca domestica, Compound 8 can also significantly enhance the insecticidal activity of imidacloprid at low concentrations, and the maximum synergy ratio can reach 6 times or more.

Secondly, the synergistic effect of Compound 8 on other neonicotinoid insecticides such as acetamiprid, thiacloprid, and clothianidin was tested in American cockroaches and brown planthopper. The results are shown in Table 2A, Table 2B and Figure 1.

Table 2A Synergistic effect of compound 8 on imidacloprid, acetamiprid, thiacloprid, clothianidin (American cockroach)

Note: The test concentration of the pesticide in the table is 2 μg/worm.

Table 2B Synergistic effect of compound 8 on imidacloprid, acetamiprid, thiacloprid, clothianidin (brown planthopper)

Note: The test concentration of the pesticide in the table is 2.5 ng/worm.

As can be seen from Table 2A, Table 2B and Figure 1, Compound 8 also has a significant synergistic effect on other neonicotinoid insecticides such as acetamiprid, thiacloprid, and clothianidin. In the American cockroach, 3.75 μg/worm compound 8 was mixed with acetamiprid, thiacloprid or clothianidin respectively, and the mortality of the test insects was 2.6 to 3.5 times that of the three insecticides alone. In the brown planthopper, 2.5 ng/worm compound 8 was mixed with acetamiprid, thiacloprid or clothianidin, respectively, and the mortality of the test insects was at least 2.6 times that of the three insecticides alone.

Example 7: Synergistic Example of Compound 9

Test agent

Insecticides: imidacloprid, acetamiprid, thiacloprid, and clothianidin were purchased from Sigma-Aldrich, St. Louis, MO, USA.

Synergist: Compound 9:

2. Bioassay: The method is the same as above.

3. Data processing: The method is the same as above.

First, the synergistic effect of compound 9 on imidacloprid was tested in brown planthopper, Laodelphax striatellus, B. tabaci, Aphis gossypii, American cockroach and Musca domestica. The results are shown in Table 3.

Table 3 Synergistic effect of compound 9 on imidacloprid in different insects

Note: a indicates the same unit

It can be seen from Table 3 that in a variety of agricultural pests and sanitary pests, low concentration of compound 9 can significantly reduce the LD ₅₀ /LC _{50 of} imidacloprid, and has a strong synergistic effect.

In the brown planthopper, when the compound 9 with a concentration greater than 0.75 ng/worm was mixed with imidacloprid, the insecticidal activity of imidacloprid was significantly enhanced; when the concentration was 2.5 ng/worm, the synergistic effect peaked, and the synergistic multiple was 6.85 times.

In the American cockroach, when the compound 9 with a concentration greater than 1.75 μg/worm was mixed with imidacloprid, the insecticidal activity of imidacloprid was significantly enhanced; when the concentration was 3.75 μg/worm, the synergistic effect peaked, and the synergistic multiple was 4.99 times.

Among the pests such as Laodelphax striatellus, B. tabaci, Aphis gossypii and Musca domestica, Compound 9 can also significantly enhance the insecticidal activity of imidacloprid at low concentrations, and the maximum synergy ratio can reach more than 5 times.

Secondly, the synergistic effect of compound 9 on other neonicotinoid insecticides such as acetamiprid, thiacloprid, and clothianidin was tested in American cockroaches and brown planthopper. The results are shown in Table 4A and Table 4B.

Table 4A Synergistic effect of compound 9 on imidacloprid, acetamiprid, thiacloprid, and clothianidin in American cockroach

Note: The test concentration of the pesticide in the table is 2 μg/worm.

Table 4B Synergistic effect of compound 9 on imidacloprid, acetamiprid, thiacloprid and clothianidin in brown planthopper

Note: The test concentration of the pesticide in the table is 2.5 ng/worm.

As can be seen from Table 4A and Table 4B, Compound 9 also has a significant synergistic effect on other neonicotinoid insecticides such as acetamiprid, thiacloprid, and clothianidin.

Example 8: Synergistic Example of Compound 10

Test agent

Insecticides: imidacloprid, acetamiprid, thiacloprid, and clothianidin were purchased from Sigma-Aldrich, St. Louis, MO, USA.

Synergist: Compound 10:

2. Bioassay: The method is the same as above.

3. Data processing: The method is the same as above.

First, the synergistic effect of Compound 10 on imidacloprid was tested in brown planthopper, Laodelphax striatellus, B. tabaci, Aphis gossypii, American cockroach and Musca domestica. The results are shown in Table 5.

Table 5 Synergistic effect of compound 10 on imidacloprid in different insects

Note: a indicates the same unit

It can be seen from Table 5 that in a variety of agricultural pests and sanitary pests, low concentration of Compound 10 can significantly reduce the LD ₅₀ /LC _{50 of} imidacloprid, and has a strong synergistic effect.

In the brown planthopper, when the compound 10 with a concentration greater than 0.75 ng/worm was mixed with imidacloprid, the insecticidal activity of imidacloprid was significantly enhanced; when the concentration was 2.5 ng/worm, the synergistic effect peaked, and the synergistic multiple was 6.45 times.

In the American cockroach, when the compound 10 with a concentration greater than 1.75 μg/worm was mixed with imidacloprid, the insecticidal activity of imidacloprid was significantly enhanced; when the concentration was 3.75 μg/worm, the synergistic effect peaked, and the synergistic multiple was 4.62 times.

Among the pests such as Laodelphax striatellus, B. tabaci, Aphis gossypii and Musca domestica, Compound 10 can also significantly enhance the insecticidal activity of imidacloprid at low concentrations, and the maximum synergy ratio can reach more than 4 times.

Secondly, the synergistic effect of Compound 10 on other neonicotinoid insecticides such as acetamiprid, thiacloprid, and clothianidin was tested in American cockroaches and brown planthopper. The results are shown in Table 6A and Table 6B.

Table 6A Synergistic effect of compound 10 on imidacloprid, acetamiprid, thiacloprid and clothianidin in American cockroach

Note: The test concentration of the pesticide in the table is 2 μg/worm.

Table 6B Synergistic effect of compound 10 on imidacloprid, acetamiprid, thiacloprid and clothianidin in brown planthopper

Note: The test concentration of the pesticide in the table is 2.5 ng/worm.

As can be seen from Table 6A and Table 6B, Compound 10 also has a significant synergistic effect on other neonicotinoid insecticides such as acetamiprid, thiacloprid, and clothianidin.

Example 9: Synergistic Example of Other Compounds

Test agent

Insecticide original drug: imidacloprid was purchased from Sigma-Aldrich, St. Louis, MO, USA;

Synergist: Compounds 1-7 and Compounds 11-13; for the synthesis of each compound, see CN200810207355.2.

2. Bioassay: The bioassay method of brown planthopper and American cockroach is a spot method, and the specific test method is the same as above.

3. Data processing: The method is the same as above.

The test results are shown in Table 7.

Table 7 Synergistic effects of compounds 1-7 and 11-13 on imidacloprid

Note: The ratio of compound to insecticide in the table is 2:1, where c indicates that the test concentration of the pesticide is 2.5 ng/worm; b indicates that the test concentration of the insecticide is 2 μg/worm.

Studies by the inventors have found that the concentration of the compound of the present invention as a synergist is much lower than when it exerts insecticidal activity.

The inventors studied the effective concentration of Compound 8 in the synergistic effect of imidacloprid in brown planthopper, and the inventors conducted The following three sets of tests:

1. Application of imidacloprid alone:

2. Compound 8 was administered alone: the concentration of compound 8 was 0 ng/worm, 0.05 ng/worm, 0.1 ng/worm, 0.25 ng/worm, 0.5 ng/worm, 0.75 ng/worm, 1 ng/worm, 1.25 ng/worm. 1.5ng/worm, 1.75ng/worm, 2ng/worm, 2.25ng/worm, 2.5ng/worm, 2.75ng/worm, 3ng/worm, 3.25ng/worm, 3.5ng/worm, 3.75ng/worm, 4ng /worm, 4.25ng/worm, 4.5ng/worm

3. Combination of compound 8 and imidacloprid; when compound 8 and imidacloprid are combined, the concentration of compound 8 is 0 ng/worm, 0.05 ng/worm, 0.1 ng/worm, 0.25 ng/worm, 0.5 ng/worm, 0.75 ng/worm. , 1ng/worm, 1.25ng/worm, 1.5ng/worm, 1.75ng/worm, 2ng/worm, 2.25ng/worm, 2.5ng/worm, 2.75ng/worm, 3ng/worm, 3.25ng/worm, 3.5ng / worm, 3.75 ng / worm, 4 ng / worm, 4.25 ng / worm, 4.5 ng / worm; the amount of imidacloprid is always 2.5 ng / worm.

The method for determination of brown planthopper is a spot method, and the specific test method is the same as above.

The results are shown in Figure 2. The results showed that for the brown planthopper, when 1 ng/worm compound 8 was combined with 2.5 ng/worm imidacloprid, the mortality of the test insects increased to about 50%, which was significantly higher than that of imidacloprid alone. Rate - 20%. However, the application of compound 8 only has a certain killing effect on brown planthopper, even at a concentration greater than 4.5 ng/worm.

It can be seen that the effective concentration of the compound of the present invention as an insecticide synergist is much lower than the concentration at which it exerts insecticidal activity.

Synergistic mechanism

The inventors studied the synergistic mechanism of the compound of formula (1) (such as compound 8) by radioligand binding experiments and electrophysiological experiments. The results indicate that the compound is a partial agonist of the insect nicotinic acetylcholine receptor and can competitively inhibit the binding of [H ³ ] imidacloprid to the receptor. The compound has agonist activity against the Nlα1/rβ2 receptor expressed in Xenopus oocytes and the nicotinic acetylcholine receptor in the American scorpion neuron cells, but the activity is poor. Further research indicates that the compound exerts synergistic effect by selectively extending the opening time of the receptor ion channel caused by a part of known insecticides (such as imidacloprid) and increasing the sensitivity of the receptor to the insecticide.

All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the In addition, it should be understood that various modifications and changes may be made by those skilled in the art in the form of the appended claims.

Claims (11)

1. The use of an eight-membered oxygen bridge heterocyclic compound as an insecticide synergist, characterized in that the octamethoxy bridged heterocyclic compound is a compound represented by the formula (1), or an optical isomer thereof, a cis-trans isomer, or a pesticidally acceptable salt thereof;

   

   In the formula:

   R ₁ is H, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, nitrogen, oxygen and/or sulfur a five- or six-membered heterocyclic group, a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted phenyl group; said substitution means selected from the group consisting of Substituted by one or more substituents: halogen, C _1-4 haloalkyl or C _1-4 chloroalkoxy;

   R ₂ , R ₃ are each independently H, C _1-6 alkyl, allyl, benzyl, C _1-4 alkoxy-C _1-4 alkyl, C _1-4 alkoxy-carbonyl, Phenoxycarbonyl, C _2-6 alkynyl-carbonyl, C _2-3 alkenyl-carbonyl, C _3-6 cycloalkyl-carbonyl, benzoyl or by one or more selected from halogen atoms, C _1-4 a benzoyl group substituted with a substituent of an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 alkyl-carbonyl group, a furancarbonyl group, an N,N-dimethylcarbonyl group, or an R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -;

   R ₄ , R ₅ , R ₆ are each independently H, saturated or unsaturated C _1-4 alkyl, halogen, C _1-8 saturated or unsaturated alkoxy, halogenated C _1-4 saturated or unsaturated Alkoxy, C _1-4 alkyl-carbonyl, C _1-8 alkyl-ester, C _1-4 alkyl-sulfonate, phenyl or benzyl;

   Y is C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, benzyl, nitro, cyano, trifluoromethyl Base, trifluoroacetyl or trifluoromethanesulfonyl.
2. The use according to claim 1, wherein R _{1 is} selected from the group consisting of pyridyl, thiazolyl, tetrahydrofuranyl, phenyl, C _1-6 alkyl or C _1-6 alkoxy.
3. The use according to claim 1, wherein R ₂ and R ₃ are each independently H or C _1-2 alkyl, or R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -.
4. The use according to claim 1, wherein R ₄ , R ₅ and R ₆ are each independently H.
5. The use according to claim 1, wherein Y is a nitro group, a cyano group, a trifluoromethyl group, a trifluoroacetyl group or a trifluoromethanesulfonyl group.
6. The use according to claim 1, wherein the insecticide is a neonicotinoid insecticide.
7. The use according to claim 6, wherein the effective concentration of the octa-oxy bridged heterocyclic compound is from 0.5 to 2500 mg/L; and/or the octa- oxy bridged heterocyclic compound and the neonicotine The weight ratio of the insecticide is 1:50 to 100:1.
8. An eight-membered oxygen bridged heterocyclic compound, characterized in that the eight-membered oxygen bridged heterocyclic compound is a compound represented by the formula (1), or an optical isomer thereof, a cis-trans isomer thereof, or a pesticide thereof a salt that is acceptable for learning;

   

   In the formula:

   When R ₁ is H, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy,

   R ₂ , R ₃ are each independently H, C _1-6 alkyl, allyl, benzyl, C _1-4 alkoxy-C _1-4 alkyl, C _1-4 alkoxy-carbonyl, Phenoxycarbonyl, C _2-6 alkynyl-carbonyl, C _2-3 alkenyl-carbonyl, C _3-6 cycloalkyl-carbonyl, benzoyl or by one or more selected from halogen atoms, C _1-4 a benzoyl group substituted with a substituent of an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 alkyl-carbonyl group, a furancarbonyl group, an N,N-dimethylcarbonyl group, or an R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -;

   R ₄ , R ₅ , R ₆ are each independently H, saturated or unsaturated C _1-4 alkyl, halogen, C _1-8 saturated or unsaturated alkoxy, halogenated C _1-4 saturated or unsaturated Alkoxy, C _1-4 alkyl-carbonyl, C _1-8 alkyl-ester, C _1-4 alkyl-sulfonate, phenyl or benzyl;

   Y is C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, benzyl, nitro, cyano, trifluoromethyl Base, trifluoroacetyl or trifluoromethanesulfonyl;

   or

   When R ₁ is a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted benzene group The substituent refers to being substituted with one or more substituents selected from the group consisting of halogen, C _1-4 haloalkyl or C _1-4 chloroalkoxy;

   R ₂ , R ₃ are each independently H, C _1-6 alkyl, allyl, benzyl, C _1-4 alkoxy-C _1-4 alkyl, C _1-4 alkoxy-carbonyl, Phenoxycarbonyl, C _2-6 alkynyl-carbonyl, C _2-3 alkenyl-carbonyl, C _3-6 cycloalkyl-carbonyl, benzoyl or by one or more selected from halogen atoms, C _1-4 a benzoyl group substituted with a substituent of an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 alkyl-carbonyl group, a furancarbonyl group, an N,N-dimethylcarbonyl group, or an R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -;

   R ₄ , R ₅ , R ₆ are each independently H, saturated or unsaturated C _1-4 alkyl, halogen, C _1-8 saturated or unsaturated alkoxy, halogenated C _1-4 saturated or unsaturated Alkoxy, C _1-4 alkyl-carbonyl, C _1-8 alkyl-ester, C _1-4 alkyl-sulfonate, phenyl or benzyl;

   Y is C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy;

   or

   When R ₁ is phenyl or chlorophenyl, R ₂ and R ₃ together form -CH ₂ -CH ₂ -, and R ₄ , R ₅ and R ₆ are each independently H and Y is a nitro group.
9. An agricultural composition comprising the active ingredient (a): a compound represented by the formula (1), or an optical isomer thereof, a cis-trans isomer thereof, or a pesticide-acceptable salt thereof; Active ingredient (b): insecticide; and active The weight ratio of the component (a) to the active ingredient (b) is 1:100 to 100:1;

   

   In the formula:

   R ₁ is H, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, nitrogen, oxygen and/or sulfur a five- or six-membered heterocyclic group, a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted phenyl group; said substitution means selected from the group consisting of Substituted by one or more substituents: halogen, C _1-4 haloalkyl or C _1-4 chloroalkoxy;

   R ₂ , R ₃ are each independently H, C _1-6 alkyl, allyl, benzyl, C _1-4 alkoxy-C _1-4 alkyl, C _1-4 alkoxy-carbonyl, Phenoxycarbonyl, C _2-6 alkynyl-carbonyl, C _2-3 alkenyl-carbonyl, C _3-6 cycloalkyl-carbonyl, benzoyl or by one or more selected from halogen atoms, C _1-4 a benzoyl group substituted with a substituent of an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, a C _1-4 alkyl-carbonyl group, a furancarbonyl group, an N,N-dimethylcarbonyl group, or an R ₂ and R ₃ together constitute -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -;

   R ₄ , R ₅ , R ₆ are each independently H, saturated or unsaturated C _1-4 alkyl, halogen, C _1-8 saturated or unsaturated alkoxy, halogenated C _1-4 saturated or unsaturated Alkoxy, C _1-4 alkyl-carbonyl, C _1-8 alkyl-ester, C _1-4 alkyl-sulfonate, phenyl or benzyl;

   Y is C _1-6 alkyl, C _1-6 alkoxy, C _1-6 halogenated alkyl, C _1-6 halogenated alkoxy, benzyl, nitro, cyano, trifluoromethyl Base, trifluoroacetyl or trifluoromethanesulfonyl.
10. The agricultural composition according to claim 9, wherein the agricultural composition is a solution, an emulsion, a suspension, a powder, a foaming agent, a paste, a granule, an aerosol, and is impregnated with an active ingredient. Natural and synthetic materials, microcapsules, coatings, formulations for use with combustion devices, ULV cold mist or Warm mist formulations.
11. Use of the agricultural composition according to claim 9 or a compound according to claim 8 for killing or preventing agricultural pests, sanitary pests and pests harmful to animal health; or for killing or preventing Pesticide compositions for agricultural pests, sanitary pests and pests that are harmful to animal health.

Images