Pyridino [1, 2-a] pyrimidine mesoion derivative containing alkynyl cyano structure as well as preparation and application of pyridino [1, 2-a] pyrimidine mesoion derivative

Abstract

The invention relates to a pyridino [1, 2-a] pyrimidine mesoion derivative containing an alkynyl cyano structure as well as a preparation method and application of the pyridino [1, 2-a] pyrimidine mesoion derivative. The compound disclosed by the invention has a structure shown in a formula [I], has excellent insecticidal activity on spodoptera frugiperda, prodenia litura, beet armyworm, ostrinia nubilalis, cutworm, plant hopper, green peach aphid, aphis avenae and the like, and can be used for preparing drugs or medicaments for preventing and treating pests such as spodoptera frugiperda, prodenia litura, beet armyworm, ostrinia nubilalis, cutworm, plant hopper, green peach aphid and the like. The structure and the preparation process are simple, and the production cost is low.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of chemical industry and pesticides, in particular to pyrido[1,2-a]pyrimidine ionic derivatives containing alkynyl cyano structure and a preparation method thereof, and the application of pyrido[1,2-a]pyrimidine ionic derivatives containing alkynyl cyano structure in the preparation of drugs for preventing and treating pests such as Spodoptera frugiperda, Spodoptera litura, Spodoptera exigua, Ostrinia nubilalis, Agrotis ypsilon, planthoppers and Myzus persicae, and Aphis craccivora. BACKGROUND

[0002] In recent years, due to the long-term use of chemical insecticides, the resistance of pests has increased exponentially, and serious resistance to commonly used insecticides has occurred. Hemipteran pests such as planthoppers, aphids and lepidopteran pests such as Chilo suppressalis, Plutella xylostella and Spodoptera frugiperda are important pest groups in agricultural production and are also the most resistant pests. Insecticide resistance has become a major challenge in global pest management.

[0003] Rice is one of the staple foods of the Chinese people, with the second largest planting area in the world and the largest yield in the world. More than 70% of the population are rice-based. In recent years, due to climate factors, changes in farming systems, lack of resistance in rice varieties, and deterioration of ecological conditions and increasing insecticide resistance, rice planthoppers (Nilaparvata lugens) have become the most serious pests in global rice production and one of the important biological factors limiting rice production. China is a high-incidence and frequent-occurrence area of rice pests and diseases. At present, the main drug for controlling rice planthoppers is neonicotinoid insecticide, which accounts for about 25% of the entire insecticide market. Due to the excessive and frequent use of traditional neonicotinoid insecticides, resistance and bee toxicity problems have become prominent, increasing the amount of pesticide use and being detrimental to environmental protection. Therefore, it is urgent to develop new insecticides that are not cross-resistant to existing pesticides, have novel modes of action, and are lowly toxic to beneficial insects such as bees.

[0004] Spodoptera frugiperda (Sf) is a global major agricultural invasive pest that can damage corn, rice, sorghum, sugarcane, peanuts, soybeans and other non-food crops, and is listed in the "List of Class I Crop Pests" in China. Since its invasion in December 2018, Sf has rapidly spread to major agricultural production areas in China, posing a serious threat to the safe production of important food crops such as corn in China. Hainan, Taiwan, southern Tibet, southwestern Yunnan, most of Guangxi, Guangdong, Fujian, Zhejiang, Jiangxi and eastern Hunan are highly suitable areas for Sf, which can reproduce throughout the year and has become a common pest through seasonal migration between north and south China. According to the Arthropod Pesticide Resistance Database (APRD), Sf has developed resistance to 47 insecticidal active ingredients worldwide. Spodoptera frugiperd ​

[0005] In summary, with the increasing prominence of resistance to major crop pests in my country leading to a continuous increase in pesticide use, there is an urgent need to develop insecticides with novel structures, high efficiency, low risk, and unique mechanisms of action to address practical problems such as the aging of pesticide varieties and formulations, the intensification of pesticide resistance, and the shortage of new formulations for the control of major crop pests in China.

[0006] In 2009, Holyoke et al. of DuPont (Corteva) first disclosed the synthesis and insecticidal activity of pyrido[1,2-a]pyrimidine mesoionic compounds in patent WO2009099929A1. These compounds possess novel structures, no cross-resistance with existing pesticides, and low toxicity to beneficial insects such as bees. They are highly effective against diamondback moth, green peach aphid, cotton aphid, and rice brown planthopper. Structure-activity relationship analysis shows that pyrido[1,2-a]pyrimidine... a The pyrimidine parent ring exhibits superior activity compared to thiazole or imidazopyrimidine rings; the 3-position benzene ring and its 3-position derivatization help maintain high activity.

[0007] In 2011, Holyke et al. disclosed a class of metronidazole compounds in patent WO2011017342A2. Some of these compounds achieved 100% mortality against diamondback moth, fall armyworm, and cotton aphid at 10 mg / L, and dichloromezotiazine was successfully commercialized. Studies showed that compounds with a 2-chlorothiazol-5-ylmethyl group at position 1 and a methyl group at position 9 exhibited optimal activity against lepidopteran pests, demonstrating a "magic methyl" effect; substituted phenyl groups at position 3 also showed excellent control efficacy. In 2012, the same company reported pyridopyrimidine metronidazole compounds containing diaryl groups in patent WO2012106495A1, which were effective against lepidopteran, homoptera, and tsandroptera pests. Some compounds achieved 100% mortality against diamondback moth and fall armyworm at 2 mg / L, and over 80% mortality against green peach aphid and potato leafhopper at 10 mg / L.

[0008] The cyano group is an extremely important functional group in pesticide development, possessing strong electron-withdrawing properties and offering the following advantages: its small spatial volume allows it to penetrate deep into target proteins and interact with amino acid residues through hydrogen bonds and π-π bonds, significantly enhancing the compound's biological activity. Furthermore, the cyano group can improve the compound's metabolic stability in vivo. Numerous pesticides contain cyano groups. A statistical analysis of 576 crop protection pesticides worldwide revealed that 45 contained cyano groups, accounting for 7.8%. Of these 45 cyano-containing pesticides, 26 were insecticides, representing 57.78%.

[0009] In 2019, Li Zhong et al. reported in Chinese Chemical Letters (DOI: 10.1016 / j.cclet.2018.05.013) the necessary binding mode of highly insecticidal neonicotinoid compounds—the H bond of the water bridge. They designed and synthesized 24 neonicotinoid compounds, and then conducted bioassays and modeling of their insecticidal activity. Among the nine fragments that mimic the water bridge, the cyano-substituted compounds showed better aphid-killing activity than the other fragments. Therefore, the cyano group was considered the best choice to mimic the water bridge fragment.

[0010] Based on the above research background, some known pest control agents on the market are highly toxic, exhibit severe resistance, or damage ecosystems through their long-term persistence. In this context, although numerous insecticides, such as WO2011017342A2 and WO2021151034A1, disclose metronidicides, there is still a need to develop novel pest control agents with low toxicity and low persistence. Therefore, this study retains pyridine and [1,2- a Based on the active pyrimidine methanogenic skeleton, a cyano group was introduced into the meta position of the 3-phenyl group to design and synthesize a class of pyrido[1,2-a]pyrimidine methanogenic derivatives containing an alkynyl cyano group. Bioassay results show that these compounds exhibit excellent insecticidal activity against lepidopteran pests such as fall armyworm, beet armyworm, corn borer, and cutworm, as well as hemipteran pests such as peach aphid and white-backed planthopper, with a broad insecticidal spectrum. This provides new ideas for the development of novel insecticides. Summary of the Invention

[0011] To address the aforementioned problems in the prior art, this invention provides a class of pyrido[1,2-a]pyrimidine mesonotropic derivatives containing an alkynyl cyano structure and a method for their preparation. The compounds exhibit excellent control effects against pests such as fall armyworm, beet armyworm, corn borer, cutworm, planthopper, and peach aphid.

[0012] Another object of the present invention is to provide a composition containing the above-mentioned derivatives.

[0013] Another object of the present invention is to provide the use of the above-described derivatives or compositions.

[0014] Another object of the present invention is to provide a method for controlling agricultural pests using the above-mentioned derivatives or compositions.

[0015] The technical solution adopted in this invention is as follows: In a first aspect, the present invention provides a pyrido[1,2-]pyridocyano-containing structure. a Pyrimidine mesonotropic derivatives, including compounds having the general formula [I] or their stereoisomers, N-oxides or their salts, wherein the structural formula [I] is as follows: Among them, Q1 and Q2 independently represent O or S respectively; X can represent C or N independently; R5 represents, independently, cyanoalkyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted thiazolyl, or substituted or unsubstituted pyridinyl. R1, R2, R3, R4, and R6 independently represent hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic, -OR8, -(CO)R8, -(CO)OR8, -(CO)N(R8)2, -S(O)nR8, or -N(R8)2, wherein the substituted alkyl, substituted alkenyl, or substituted alkynyl means optionally substituted by at least one group selected from halogen, cycloalkyl, aryl, heterocyclic, -OR8, -(CO)OR8, -S(O)nR8, or -N(R8)2; n is 0, 1, or 2; R8 can independently represent hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, cycloalkylalkyl, substituted or unsubstituted aryl, arylalkyl, substituted or unsubstituted heterocyclic or heterocyclic alkyl, wherein the substituted alkyl, substituted alkenyl or substituted alkynyl means that it is optionally substituted by at least one group selected from halogen or alkoxy; The substituted cycloalkyl, substituted heterocyclic, or substituted aryl group refers to a group optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, ynyl, cycloalkyl, haloalkyl, haloalkenyl, haloynyl, -OR7, -SR7, -(CO)R7, -(CO)OR7, -(CO)N(R7)2, -(CS)N(R7)2, -(SO)R7, or -(SO2)R7; or forming a fused ring with two adjacent carbon atoms on the ring and an unsubstituted or halogen-substituted -OCH2O-, -CH2CH2CH2O-, or -CH=CHCH=CH-; or forming a ring structure with a saturated carbon atom on the ring connected to both ends of an unsubstituted or halogen-substituted -OCH2CH2O-. R7 independently represents hydrogen, deuterium, alkyl, haloalkyl, phenyl, or a phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylacyl, alkoxy, or haloalkoxy.

[0016] In one specific embodiment, R5 independently represents cyanoalkyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted thiazolyl, and substituted or unsubstituted pyridinyl. R1, R2, R3, R4, and R6 independently represent hydrogen, halogen, cyano, nitro, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C2-C8 alkynyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic, -OR8, -(CO)R8, -(CO)OR8, -(CO)N(R8)2, -S(O)nR8, or -N(R8)2, wherein the substituted C1-C8 alkyl, substituted C2-C8 alkenyl, or substituted C2-C8 alkynyl is optionally substituted by at least one group selected from halogen, C3-C8 cycloalkyl, aryl, heterocyclic, -OR8, -(CO)R8, -S(O)nR8, or -N(R8)2; R8 independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, substituted or unsubstituted C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, substituted or unsubstituted aryl, aryl C1-C8 alkyl, substituted or unsubstituted heterocyclic or heterocyclic C1-C8 alkyl, wherein the C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl means optionally substituted by at least one group selected from halogen or C1-C8 alkoxy; The substituted C3-C8 cycloalkyl, substituted heterocyclic, or substituted aryl group refers to a group optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 ynyl, -OR7, -SR7, -(CO)R7, -(CO)OR7, -(CO)N(R7)2, -(CS)N(R7)2, -(SO)R7, or -(SO2)R7; or two adjacent carbon atoms on the ring form a fused ring with an unsubstituted or halogen-substituted -OCH2O-, -CH2CH2CH2O-, or -CH=CHCH=CH-; or a saturated carbon atom on the ring is connected to both ends of an unsubstituted or halogen-substituted -OCH2CH2O- to form a ring structure; R7 independently represents hydrogen, deuterium, alkyl, haloalkyl, phenyl, or a phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylacyl, alkoxy, or haloalkoxy.

[0017] In another specific embodiment, R5 independently represents cyanoalkyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted thiazolyl, and substituted or unsubstituted pyridinyl. R1, R2, R3, R4, and R6 independently represent hydrogen, halogen, cyano, nitro, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic, -OR8, -(CO)R8, -(CO)OR8, -(CO)N(R8)2, -S(O)nR8, or -N(R8)2, wherein the substituted C1-C6 alkyl, substituted C2-C6 alkenyl, or substituted C2-C6 alkynyl is optionally substituted by at least one group selected from halogen, C3-C6 cycloalkyl, aryl, heterocyclic, -OR8, -(CO)R8, -S(O)nR8, or -N(R8)2; R8 independently represents hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, substituted or unsubstituted aryl, aryl C1-C6 alkyl, substituted or unsubstituted heterocyclic or heterocyclic C1-C6 alkyl, wherein the substituted C1-C6 alkyl, substituted C2-C6 alkenyl or substituted C2-C6 alkynyl means optionally substituted by at least one group selected from halogen or C1-C6 alkoxy; The substituted C3-C6 cycloalkyl, substituted heterocyclic, or substituted aryl group refers to a group optionally substituted by at least one group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 ynyl, -OR7, -SR7, -(CO)R7, -(CO)OR7, -(CO)N(R7)2, -(CS)N(R7)2, -(SO)R7, or -(SO2)R7; or two adjacent carbon atoms on the ring form a fused ring with an unsubstituted or halogenated -OCH2O-, -CH2CH2CH2O-, or -CH=CHCH=CH-; or a saturated carbon atom on the ring is connected to both ends of an unsubstituted or halogenated -OCH2CH2O- to form a ring structure; R7 independently represents hydrogen, deuterium, alkyl, haloalkyl, phenyl, or a phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylacyl, alkoxy, or haloalkoxy.

[0018] In the definitions of compounds shown in the above general formulas and in all the following structural formulas, the technical terms used, whether alone or in compound terms, represent the following substituents: alkyl groups having more than two carbon atoms can be straight-chain or branched. For example, the alkyl group in "alkyl" can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, for example, C1 alkyl-methyl, C2 alkyl-ethyl, C3 alkyl-propyl such as n-propyl or isopropyl, C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl, C5 alkyl-pentyl such as n-pentyl, C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, alkenyl groups are, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Alkynyl groups are, for example, ethynyl, propynyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methylbut-3-yn-1-yl. Multiple bonds can be in any position in each unsaturated group. Cycloalkyl groups are carbocyclic saturated ring systems having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Similarly, cycloalkenyl groups are monocyclic alkenyl groups having, for example, three to six carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, wherein double bonds can be in any position. Halogens are fluorine, chlorine, bromine, or iodine.

[0019] Unless otherwise specified, the term "aryl" in this invention includes, but is not limited to, phenyl, naphthyl, and... , The "heterocyclic group" includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups. , , , , , , , , , , , , , , , , , , , , , , , .

[0020] , , , , , And, including but not limited to, heteroaryl groups, i.e., aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally fused with benzo[a] rings, wherein 1 to 4 (e.g., 1, 2, 3, or 4) heteroatoms are selected from oxygen, nitrogen, and sulfur, for example , , , , , , , , or .

[0021] The terms "optional" or "optionally" mean that the event or situation described below may or may not occur, and the description includes instances where said event or situation occurs and instances where said event or situation does not occur. For example, the term "optionally...substituted" means that the specified atom or group is unsubstituted or substituted by one or more substituents. If a group is substituted by a group, this should be understood to mean that the group is substituted by one or more groups of the same or different selected from those groups mentioned. Furthermore, the same or different substitution characters contained in the same or different substituents are chosen independently and may be the same or different. This also applies to ring systems formed from different atoms and units. Meanwhile, the scope of the claims excludes compounds that are chemically unstable under standard conditions, as known to those skilled in the art.

[0022] Furthermore, unless otherwise specified, the phrase "replaced by at least one group" in this invention refers to being replaced by, for example, 1, 2, 3, 4, or 5 groups; groups without specific attachment positions (including heterocyclic groups, aryl groups, etc.) can be attached at any position, including positions attached to C or N; if it is substituted, the substituent can also be substituted at any position, as long as it conforms to the rules of chemical bond attachment. For example, a heteroaryl group substituted by one methyl group. Can represent , , , wait.

[0023] If various functional groups are present, the present invention also includes any ketone and enol tautomer forms, mixtures thereof, and salts thereof.

[0024] Stereoisomers can be obtained from mixtures prepared by optical resolution. Similarly, stereoisomers can be selectively prepared using stereoselective reactions and optically active starting materials and / or auxiliaries. For optical resolution, conventional methods (see Textbooks of Stereochemistry) can generally be used, such as physical methods for resolving mixtures into diastereomers, including crystallization, chromatography, especially column chromatography and high-performance liquid chromatography, distillation under reduced pressure as needed, extraction, and other methods, typically employing chromatographic separation on a chiral solid phase, which can separate the residual mixture of enantiomers. Suitable for preparative or industrial scales are methods such as crystallizing diastereomers, which can be obtained from the compound using optically active acids, and, if acidic groups are present, using optically active bases as needed.

[0025] Secondly, another embodiment of this application is the pyrido[1,2-]pyridocyano-containing pyridinium[1,2- a A method for preparing pyrimidine mesonotropic derivatives, including compounds having the general formula [I] or their stereoisomers, N-oxides or their salts, comprising the following steps: Where L1 and L2 represent halogens or -OH, -O-CH3, and -O-CH2CH3, respectively, and the definitions of substituents X, M, Q1, Q2, R1, R2, R3, R4, R5, and R6 are as described above; In one specific embodiment, the reaction is carried out under alkaline and solvent conditions.

[0026] Preferably, the reaction is carried out in the presence of a base and a solvent; More preferably, the base is selected from at least one of inorganic or organic bases. In one specific embodiment, the inorganic base includes, but is not limited to, at least one of NaH, KH, NaOH, KOH, Na2CO3, K2CO3, Cs2CO3, KF, and CsF; the organic base includes, but is not limited to, at least one of pyrazole, triethylamine, N,N-diisopropylethylamine, pyridine, DIEA, potassium trimethylsilanol, AcOK, AcONa, MeONa, EtONa, t-BuONa, and t-BuOK.

[0027] More preferably, in one embodiment, the solvent is selected from at least one of DCM, diethyl ether, DMF, tetrahydrofuran, methyltetrahydrofuran, toluene, xylene, diphenyl ether, or dioxane.

[0028] The preparation methods of the compounds described in this invention can be found in WO2011017342A2, WO2021151034A1, etc.

[0029] The present invention also relates to an intermediate, as shown in formula [II] above.

[0030] Thirdly, the present invention also relates to pyrido[1,2-]pyridocyano containing an alkynyl cyano structure. a ]Pyrimidine mesonotropic derivatives or pyrido[1,2- a Use of pyrimidine metronid derivative compositions in the preparation of pesticides for pest control.

[0031] This invention provides a composition comprising pyrido[1,2-]pyridocyano containing an alkynyl cyano group. a The composition comprises pyrimidine mesonotropic derivatives and agricultural adjuvants; the formulation of the composition is selected from emulsifiable concentrates (EC), powders (DP), wettable powders (WP), granules (GR), aqueous solutions (AS), suspensions (SC), ultra-low volume sprays (ULV), soluble powders (SP), microcapsules (MC), fumigants (FU), emulsions (EW), and water-dispersible granules (WG).

[0032] The present invention also provides an insecticidal composition comprising at least one of a compound of formula [I] or its stereoisomer, its N-oxide or its salt; in one embodiment, it further comprises a formulation adjuvant; in another embodiment, it further comprises other active ingredients.

[0033] This invention provides a method for controlling pests, the method comprising exposing the pest or its environment to a biologically effective amount of the aforementioned pyrido[1,2-]pyridyl-cyano-containing ...cyano-containing pyridyl-cyano-cyano-containing pyridyl-cyano-cyano-containing pyridyl-cyano-cyano-cyano-containing pyridyl-cyano-cyano-cyano-containing pyridyl-cyano-cyano-cyano-cyano-containing pyridyl-cyano-cyano-cyano-cyano-cyano-cyano-cyano-cyano-cyano-cyano-cyano-cyano-cyano a [I] Pyrimidine mesonoionic derivatives of the formula [I] or their stereoisomers, their N-oxides or their salts, or combinations thereof.

[0034] As an embodiment of the present invention, it is also worth noting the composition comprising any of the compounds in the foregoing embodiments and any other embodiments described herein, and any combination thereof, and at least one additional component and / or formulation adjuvant and / or at least one active ingredient (i.e., a biologically active compound or reagent), said additional component being selected from surfactants, solid diluents and liquid diluents.

[0035] Useful formulations include liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspensions), etc., which can optionally be thickened into gels. Aqueous liquid compositions are generally categorized as soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, and suspensions. Non-aqueous liquid compositions are generally categorized as emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0036] Solid compositions are generally available in the form of powders, granules, pellets, pellets, pellets, lozenges, tablets, and filled films (including seed coatings), and can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredients can be encapsulated (micro)capsules and further formed into suspensions or solid formulations; alternatively, the entire active ingredient formulation can be encapsulated (or “coated”). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrates and dry granule formulations. High-concentration compositions are primarily used as intermediates for other formulations.

[0037] Fourthly, in this invention, the compound of formula [I] is a methanogenic inner salt. Furthermore, the "inner salt," also known in the art as an "amphoteric ion," is an electrically neutral molecule, but according to valence bond theory, it carries both positive and negative charges in each valence bond structure of different atoms. Moreover, the molecular structure of the compound of formula [I] can be represented by the following six valence bond structures: Each carries both positive and negative charges on different atoms. Due to this resonance, the compound of formula [I] is also described as a “medium ion.” Although for the sake of brevity, the molecular structure of formula [I] is described as a single-valent structure in this paper, this specific valence structure should be understood as representative of all six valence structures involved in the intramolecular linkages of the compound of formula [I]. Therefore, unless otherwise specified, references to formula [I] in this paper refer to all six applicable valence structures as well as other structures (e.g., those based on molecular orbital theory).

[0038] The compounds of the present invention can exist in the form of one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, transisomers, and geometric isomers. Those skilled in the art will recognize that a stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to other stereoisomers or when isolated from other stereoisomers. Furthermore, those skilled in the art know how to isolate, enrich, and / or selectively prepare said stereoisomers. The compounds of the present invention can exist as mixtures of stereoisomers, individual stereoisomers, or as optically active forms.

[0039] Because bond rotation is restricted due to steric hindrance, the compounds of this invention can exist in one or more conformational isomers. This invention includes mixtures of conformational isomers. Furthermore, this invention includes compounds enriched in one conformational isomer relative to other conformational isomers.

[0040] Fifthly, the present invention provides pyrido[1,2-]pyridocyano containing the alkynyl cyano structure. aUse of pyrimidine metronid derivatives or the composition in the preparation of drugs for the control of agricultural pests and diseases; wherein the agricultural pests and diseases are lepidopteran and hemiptera pests.

[0041] Preferably, the agricultural pests are fall armyworm, beet armyworm, corn borer, cutworm, planthopper and peach aphid.

[0042] In a sixth aspect, the present invention provides a method for preventing and controlling agricultural pests and diseases, wherein the compound or its salt, or the composition thereof, is applied to a harmful substance or its habitat; preferably, the agricultural pests and diseases are lepidopteran and hemiptera pests; more preferably, the agricultural pests are fall armyworm, beet armyworm, corn borer, cutworm, planthopper and peach aphid.

[0043] In a seventh aspect, the present invention provides a method for protecting plants from agricultural pests and diseases, comprising inducing the pests to react with the pyridine containing the alkynyl cyano structure [1,2- a Method steps for contacting pyrimidine mesonotropic derivatives or the composition described above.

[0044] The beneficial effects of this invention are: In this invention, the compounds have novel structures containing cyano groups with broad biological activity. The compounds provided by this invention exhibit excellent insecticidal activity against lepidopteran and hemiptera pests. Among the compounds synthesized in this invention, some exhibit excellent insecticidal activity against pests such as fall armyworm, beet armyworm, corn borer, cutworm, planthopper, and peach aphid. Some compounds show excellent insecticidal activity even at low doses (10... μ Even under conditions of g / mL, it still exhibits excellent insecticidal activity. Therefore, the compound provided by this invention can improve the problem of high-dose application, fundamentally reduce the dosage and cost of application, and reduce pest resistance. Specific implementation methods The present invention will be further illustrated below through examples and embodiments. It should be understood that the methods described in the embodiments are merely illustrative and not intended to limit the invention. Simple modifications to the preparation methods of the present invention within the framework of the present invention's concept are all within the scope of protection claimed by the present invention. All raw materials and solvents used in the embodiments are commercially available reagents of the corresponding purity.

[0045] Given the economic efficiency and diversity of the compounds, we preferentially synthesized a number of compounds, some of which are listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustration of the present invention and do not limit the invention. Those skilled in the art should not interpret this as limiting the scope of the above-mentioned subject matter of the invention to the following compounds.

[0046] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The raw materials can be commercially available or prepared by methods known in the literature or as detailed in the description. Those skilled in the art will understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although specific raw materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar raw materials and conditions. Variations or modifications to the preparation methods of the present invention, such as various isomers of the compounds, are included within the scope of the present invention. Furthermore, the preparation methods described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, protecting appropriate groups during the reaction process, etc.

[0047] The following method examples are provided to further illustrate the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further explain the invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds shown in the table below are either commercially available or can be easily prepared by those skilled in the art.

[0048] The specific synthesis steps of the representative compounds G1-G26 are as follows. The synthesis methods of other compounds protected in the molecular structure of formula [I] are similar and can be easily prepared by those skilled in the art. They will not be described in detail here.

[0049] Example 1: Preparation of compound 1-((2-chlorothiazol-5-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)phenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G1) (1) Add raw materials [1-2] (1.16 g, 13.63 mmol), cuprous iodide (265.34 mg, 1.39 mmol), and palladium dichloride bis(triphenylphosphine) (977.89 mg, 1.39 mmol) to a 100 mL Schlenk flask. After adding the raw materials, place a stir bar and purge the air in the reaction flask three times with nitrogen. Dissolve raw material [1-1] (prepared according to reference WO2024243693 A1) (4 g, 13.93 mmol) in 60 mL of ultra-dry anhydrous TEA and add it to the system under a nitrogen atmosphere. After the addition is complete, heat the system to 75 °C and react for 4–5 h. After the reaction is complete by TLC monitoring, cool the system to room temperature, concentrate under reduced pressure to remove triethylamine, dilute the residue with ethyl acetate, and add 150 mL of aqueous solution to the system. Extracted by 3 mL, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated, mixed, and separated by column chromatography to obtain 2.54 g of colorless oily liquid [1-3], with a yield of 63.90%.

[0050] NC represents cyano; (2) The intermediate [1-3] (1g, 3.51 mmol) and 15mL of methanol were added to a 50mL flask. At room temperature, NaOH (420.58 mg, 10.52 mmol) was dissolved in 5mL and added dropwise to the reaction system. The reaction was carried out overnight at room temperature. After the reaction was completed, 150mL of water was added to dilute the mixture. The mixture was extracted once with 50mL of ethyl acetate. The pH was adjusted to 1-2 with dilute hydrochloric acid. The mixture was then extracted three times with 100mL of ethyl acetate. The organic phases were combined and washed once with saturated brine. The organic phase was dried with anhydrous sodium sulfate and evaporated to dryness to obtain 0.82 g of white solid [1-4], with a yield of 90.94%.

[0051] (3) Add intermediate [1-4] (0.82 g, 3.19 mmol) to a 50 mL flask, add 15 mL of DCM and 1 drop of catalytic DMF to a round-bottom flask, add oxalyl chloride (2.02 g, 15.94 mmol) dropwise under ice bath, and react for 2-3 h until the reaction is complete. Remove solvent under reduced pressure, add 20 mL of dichloromethane for later use. Dissolve intermediate [1-5] (0.725 g, 3.21 mmol) (prepared from raw material [1-5] according to reference CN113773319 A) and base TEA (309.64 mg, 3.06 mmol) in 15 mL of DCM, mix well, and add dropwise to the reaction system at 0 °C. After reacting for about 30 min, add 3 mL of methanol to quench the reaction, add silica gel to stir, separate the target product by chromatography column, and slurry with ethyl acetate and petroleum ether to obtain yellow solid G1310 mg, with a yield of 22.67%.

[0052] Example 2: Preparation of compound 1-((6-chloropyridin-3-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)phenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G2) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (3), where intermediates [1-5] are replaced with 6-chloro-N-2-pyridyl-3-pyridinemethylamine (prepared according to reference CN120923496 A). Example 3: Preparation of compound 3-(3-(4-cyanobut-1-yn-1-yl)phenyl)-4-oxo-1-(pyrimidin-5-ylmethyl)-4H-pyrido[1,2-a]pyrimidin-1-onthium-2-ol ester (G3) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (3), where intermediates [1-5] are replaced with N-2-pyridyl-5-pyrimidinemethylamine (prepared from reference WO2023016278 A1). Example 4: Preparation of compound 1-((2-chlorothiazol-5-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)phenyl)-9-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G4) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (3), where intermediates [1-5] are replaced with N-((2-chlorothiazo-5-yl)methyl)-3-methylpyridin-2-amine (prepared in reference JP7660866B1). Example 5: Preparation of compound 1-((2-chlorothiazo-5-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-4-methylphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G5) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (1), where intermediate [1-1] is replaced with dimethyl 2-(3-bromo-4-methylphenyl)malonate (prepared in reference WO2024243693 A1). Example 6: Preparation of compound 1-((6-chloropyridin-3-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-4-methylphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G6) Steps (1) to (3) are the same as steps (1) to (3) in Example 5. The difference lies in step (3), where intermediates [1-5] are replaced with 6-chloro-N-2-pyridyl-3-pyridinemethylamine (prepared according to reference CN120923496 A). Example 7: Preparation of compound 1-((6-chloropyridin-3-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-4-methylphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G7) Steps (1) to (3) are the same as steps (1) to (3) in Example 5. The difference lies in step (3), where intermediates [1-5] are replaced with N-2-pyridyl-5-pyrimidinemethylamine (prepared in reference WO2023016278 A1). Example 8: Preparation of compound 1-((2-chlorothiazol-5-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-4-methylphenyl)-9-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidin-1-onthiol (G8) Steps (1) to (3) are the same as steps (1) to (3) in Example 5. The difference lies in step (3), where intermediates [1-5] are replaced with N-((2-chlorothiazo-5-yl)methyl)-3-methylpyridin-2-amine (prepared in reference JP7660866B1). Example 9: Preparation of compound 1-((2-chlorothiazol-5-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-5-methylphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G9) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (1), where intermediate [1-1] is replaced with dimethyl 2-(3-bromo-5-methylphenyl)malonate (prepared in reference WO2024243693 A1). Example 10: Preparation of compound 1-((6-chloropyridin-3-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-5-methylphenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G10) Steps (1) to (3) are the same as steps (1) to (3) in Example 9. The difference lies in step (3), where intermediates [1-5] are replaced with 6-chloro-N-2-pyridyl-3-pyridinemethylamine (prepared according to reference CN120923496 A). Example 11: Preparation of compound 3-(3-(4-cyanobut-1-yn-1-yl)-5-methylphenyl)-4-oxo-1-(pyrimidin-5-ylmethyl)-4H-pyrido[1,2-a]pyrimidin-1-onthiol (G11) Steps (1) to (3) are the same as steps (1) to (3) in Example 9. The difference lies in step (3), where intermediates [1-5] are replaced with N-2-pyridyl-5-pyrimidinemethylamine (prepared from reference WO2023016278 A1). Example 12: Preparation of compound 1-((2-chlorothiazol-5-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-5-methylphenyl)-9-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidin-1-onthiol (G12) Steps (1) to (3) are the same as steps (1) to (3) in Example 9. The difference lies in step (3), where intermediates [1-5] are replaced with N-((2-chlorothiazo-5-yl)methyl)-3-methyl-pyridine-2-amine (prepared according to reference JP7660866B1). Example 13: Preparation of compound 1-((2-chlorothiazol-5-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-5-(trifluoromethoxy)phenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G13) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (1), where intermediate [1-1] is replaced with dimethyl 2-(3-bromo-5-(trifluoromethoxy)phenyl)malonate (prepared in reference WO2024243693 A1). Example 14: Preparation of compound 1-((6-chloropyridin-3-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-5-(trifluoromethoxy)phenyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G14) Steps (1) to (3) are the same as steps (1) to (3) in Example 13. The difference lies in step (3), where intermediates [1-5] are replaced with 6-chloro-N-2-pyridyl-3-pyridinemethylamine (prepared according to reference CN120923496 A). Example 15: Preparation of compound 3-(3-(4-cyanobut-1-yn-1-yl)-5-(trifluoromethoxy)phenyl)-4-oxo-1-(pyrimidin-5-ylmethyl)-4H-pyrido[1,2-a]pyrimidin-1-onthiol (G15) Steps (1) to (3) are the same as steps (1) to (3) in Example 13. The difference lies in step (3), where intermediates [1-5] are replaced with N-2-pyridyl-5-pyrimidinemethylamine (prepared in reference WO2023016278 A1). Example 16: Preparation of compound 1-((2-chlorothiazol-5-yl)methyl)-3-(3-(4-cyanobut-1-yn-1-yl)-5-(trifluoromethoxy)phenyl)-9-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidin-1-onthiol (G16) Steps (1) to (3) are the same as steps (1) to (3) in Example 13. The difference lies in step (3), where intermediates [1-5] are replaced with N-((2-chlorothiazo-5-yl)methyl)-3-methylpyridin-2-amine (prepared in reference JP7660866B1). Example 17: Preparation of compound 3-(4-chloro-3-(4-cyanobut-1-yn-1-yl)phenyl)-1-((2-chlorothiazol-5-yl)methyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G17) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (1), where intermediate [1-1] is replaced with dimethyl 2-(3-bromo-4-chlorophenyl)malonate (prepared in reference WO2024243693 A1). Example 18: Preparation of compound 3-(4-chloro-3-(4-cyanobut-1-yn-1-yl)phenyl)-1-((6-chloropyridin-3-yl)methyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G18) Steps (1) to (3) are the same as steps (1) to (3) in Example 17. The difference lies in step (3), where intermediates [1-5] are replaced with 6-chloro-N-2-pyridyl-3-pyridinemethylamine (prepared according to reference CN120923496 A). Example 19: Preparation of compound 3-(4-chloro-3-(4-cyanobut-1-yn-1-yl)phenyl)-4-oxo-1-(pyrimidin-5-ylmethyl)-4H-pyrido[1,2-a]pyrimidin-1-onthium-2-ol ester (G19) Steps (1) to (3) are the same as steps (1) to (3) in Example 17. The difference lies in step (3), where intermediates [1-5] are replaced with N-2-pyridyl-5-pyrimidinemethylamine (prepared in reference WO2023016278 A1). Example 20: Preparation of compound 3-(4-chloro-3-(4-cyanobut-1-yn-1-yl)phenyl)-1-((2-chlorothiazol-5-yl)methyl)-9-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidin-1-onthiol (G20) Steps (1) to (3) are the same as steps (1) to (3) in Example 17. The difference lies in step (3), where intermediates [1-5] are replaced with N-((2-chlorothiazo-5-yl)methyl)-3-methylpyridin-2-amine (prepared in reference JP7660866B1). Example 21: Preparation of compound 3-(3-chloro-5-(4-cyanobut-1-yn-1-yl)phenyl)-1-((2-chlorothiazol-5-yl)methyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G21) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (1), where intermediate [1-1] is replaced with dimethyl 2-(3-bromo-5-chlorophenyl)malonate (prepared in reference WO2024243693 A1). Example 22: Preparation of compound 3-(3-chloro-5-(4-cyanobut-1-yn-1-yl)phenyl)-1-((6-chloropyridin-3-yl)methyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G22) Steps (1) to (3) are the same as steps (1) to (3) in Example 21. The difference lies in step (3), where intermediates [1-5] are replaced with 6-chloro-N-2-pyridyl-3-pyridinemethylamine (prepared according to reference CN120923496 A). Example 23: Preparation of compound 3-(3-chloro-5-(4-cyanobut-1-yn-1-yl)phenyl)-4-oxo-1-(pyrimidin-5-ylmethyl)-4H-pyrido[1,2-a]pyrimidin-1-onthium-2-ol ester (G23) Steps (1) to (3) are the same as steps (1) to (3) in Example 21. The difference lies in step (3), where intermediates [1-5] are replaced with N-2-pyridyl-5-pyrimidinemethylamine (prepared in reference WO2023016278 A1). Example 24: Preparation of compound 3-(3-chloro-5-(4-cyanobut-1-yn-1-yl)phenyl)-1-((2-chlorothiazol-5-yl)methyl)-9-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidin-1-onthiol (G24) Steps (1) to (3) are the same as steps (1) to (3) in Example 21. The difference lies in step (3), where intermediates [1-5] are replaced with N-((2-chlorothiazo-5-yl)methyl)-3-methylpyridin-2-amine (prepared in reference JP7660866B1). Example 25: Preparation of compound 3-(3-chloro-4-(4-cyanobut-1-yn-1-yl)phenyl)-1-((2-chlorothiazol-5-yl)methyl)-4-oxo-4H-pyrido[1,2-a]pyrimidine-1-onthium-2-ol ester (G25) Steps (1) to (3) are the same as steps (1) to (3) in Example 1. The difference lies in step (1), where intermediate [1-1] is replaced with dimethyl 2-(4-bromo-3-chlorophenyl)malonate (prepared in reference WO2024243693 A1). Example 26: Preparation of compound 3-(3-chloro-4-(4-cyanobut-1-yn-1-yl)phenyl)-1-((2-chlorothiazol-5-yl)methyl)-9-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidin-1-onthiol (G26) Steps (1) to (3) are the same as steps (1) to (3) in Example 25. The difference lies in step (3), where intermediates [1-5] are replaced with N-((2-chlorothiazo-5-yl)methyl)-3-methylpyridin-2-amine (prepared in reference JP7660866B1). The compounds G2-G26 were purified by separating the target product using a chromatography column and then slurrying them with ethyl acetate and petroleum ether. All compounds G2-G26 were pale yellow solids with yields between 20% and 50%.

[0053] The compound's nuclear magnetic resonance hydrogen spectrum ( 1 H NMR, carbon spectrum 13 The C10 NMR and high-resolution mass spectrometry (HRMS) data are shown in Table 1.

[0054] Table 1. Spectral data of compounds G1-G26 in Examples

[0055] 2. Evaluation of biological activity After dissolving the active ingredient in acetone or DMSO, the solution was diluted with distilled water to a gradient dosage. Test insects of similar physiological state (fall armyworm, beet armyworm, corn borer, cutworm, white-backed planthopper, peach aphid, etc.) were selected and placed in disposable transparent boxes. Each box contained 10 (Lepidoptera) / 40 (Hemiptera) test insects of similar growth, along with host plant leaves (corn leaves, lotus leaves, rice seedlings, broad bean seedlings). The mixture was then sprayed using a spray tower. After spraying, a homemade breathable lid was tightly closed. This process was repeated three times, with the highest dose of acetone solution serving as a control. The treated insects were then placed in the treatment room under normal rearing conditions. The number of dead insects was checked after 48 hours, and the mortality rate was calculated using the formula: Mortality rate (%) = (Number of dead insects / Number of test insects) * 100. Representative experimental results are shown below: Example 1: Indoor bioactivity determination of target compound for controlling fall armyworm.

[0056] Second-instar fall armyworm larvae of uniform physiological condition were selected from indoor rearing. Ten larvae were chosen from each disposable transparent box. Four to five 2 cm long corn leaves were placed in each box, and spraying was performed using a spray tower. Each dosage was repeated in triplicate, with a corresponding concentration of acetone as a control. After treatment, the larvae were transferred to their rearing conditions. Results were examined after 48 hours. The mortality rate and corrected mortality rate were calculated as follows, and the activity data are shown in Table 2. Mortality rate = (Number of dead insects) / (Total number of insects treated) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 2. Insecticidal activity of the compounds in the examples against fall armyworm (2nd instar).

[0057] Insecticidal activity results showed that compounds G1, G2, G4, G5, G8, G9, G12, G13, G14, G16, G20, and G24 exhibited good insecticidal activity against fall armyworm, with most compounds showing activity at 200 μL / min. μ g / mL and 100 μ At a concentration of g / mL, the lethality against fall armyworm was 100%. Compounds G4, G16, and G24 showed a lethality of 10 g / mL. μ The mortality rate against fall armyworm remains 100% at a concentration of g / mL.

[0058] "-" indicates no data; positive controls: trifluoropyrimidine and dichloropyrimidine.

[0059] Example 2: Determination of the bioactivity of the target compound in controlling the beet armyworm indoors.

[0060] Second-instar Spodoptera litura larvae of the same physiological state, kept indoors, were selected. Ten larvae were chosen from each disposable transparent box. Four to five 2 cm long corn leaves were placed in each box, and spraying was performed using a spray tower. Each dosage was repeated in triplicate, with acetone at the corresponding concentration serving as a control. After treatment, the larvae were transferred to their original rearing conditions. Results were examined after 48 hours. The mortality rate and corrected mortality rate were calculated as follows, and the activity data are shown in Table 3. Mortality rate = (Number of dead insects) / (Total number of insects treated) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 3. Insecticidal activity of the compounds in the examples against Spodoptera litura (2nd instar).

[0061] Insecticidal activity results showed that compounds G4, G8, G12, G16, and G24 exhibited good insecticidal activity against the beet armyworm. The tested compounds showed good insecticidal activity at 100... μ At a concentration of g / mL, the lethality against *Spodoptera litura* was 100%. Compounds G4, G16, and G24 showed a lethality of 10 g / mL. μ The mortality rate against Spodoptera litura remains 100% at a concentration of g / mL.

[0062] Example 3: Indoor bioactivity determination of target compound for controlling beet armyworm.

[0063] Second-instar beet armyworms of uniform physiological condition were selected from indoor rearing. Ten insects were chosen from each disposable transparent box. Four to five 2 cm long corn leaves were placed in each box, and spraying was performed using a spray tower. Each dosage was repeated in triplicate, with a corresponding concentration of acetone as a control. After treatment, the insects were transferred to their rearing conditions. Results were examined after 48 hours. The mortality rate and corrected mortality rate were calculated as follows, and the activity data are shown in Table 4. Mortality rate = (Number of dead insects) / (Total number of insects treated) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 4. Insecticidal activity of the compounds in the examples against beet armyworm (2nd instar).

[0064] Insecticidal activity results showed that compounds G4, G8, G12, G16, and G24 exhibited good insecticidal activity against the beet armyworm. The tested compounds showed good insecticidal activity at 100... μ At a concentration of g / mL, the lethality against beet armyworm was 100%. Compounds G4, G16, and G24 showed a lethality of 10 g / mL. μ The mortality rate against beet armyworm remains 100% at a concentration of g / mL.

[0065] Example 4: Indoor bioactivity assay of target compound for controlling corn borer.

[0066] After dissolving the active ingredient in DMSO, the solution was diluted with distilled water to a gradient dosage. Second-instar corn borers of uniform physiological condition, kept indoors, were selected and placed in disposable transparent boxes. Ten corn borers of uniform growth were placed in each box, along with 4-5 leaves of host plant (corn leaves). The boxes were then sprayed using a spray tower. After spraying, the lids were tightly closed. This process was repeated three times, with the highest dose of DMSO solution serving as a control. The treated insects were then placed in the treatment room under normal rearing conditions. The number of dead insects was checked after 48 hours, and the mortality rate was calculated using the formula: Mortality Rate (%) = (Number of Dead Insects / Number of Test Insects) * 100. Representative experimental results are shown in Table 5. Mortality Rate = (Number of Dead Insects) / (Total Number of Treated Insects) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 5. Insecticidal activity of the compounds in the examples against corn borers.

[0067] Insecticidal activity results showed that compounds G4, G8, G12, G16, and G24 exhibited good insecticidal activity against the corn borer. The tested compounds showed good insecticidal activity at 100... μAt a concentration of g / mL, the lethality against corn borers was 100%. Compounds G4, G16, and G24 showed a lethality of 10 g / mL. μ The lethality against corn borers remains 100% even at a concentration of g / mL.

[0068] "-" indicates no data; positive controls: trifluoropyrimidine and dichloropyrimidine.

[0069] Example 5: Determination of the bioactivity of the target compound in controlling cutworms indoors.

[0070] Second-instar cutworms of uniform physiological condition were selected for indoor rearing, with 10 cutworms picked from each petri dish. These were placed in disposable transparent boxes, each containing 10 second-instar corn borers of uniform growth, along with host plant leaves (corn leaves). A sprayer was then used to spray the insects. After spraying, the lid was tightly closed, and the process was repeated three times. The highest dose of DMSO solution was used as a control. After treatment, the insects were transferred to their rearing conditions. Results were examined after 48 hours. The mortality rate and corrected mortality rate were calculated as follows, and the activity data are shown in Table 6. Mortality rate = (Number of dead insects) / (Total number of insects treated) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 6. Insecticidal activity of the compounds in the examples against cutworms

[0071] Insecticidal activity results showed that compounds G4, G8, G12, G16, and G24 exhibited good insecticidal activity against cutworms. Compounds G4, G16, and G24 showed good insecticidal activity at 10... μ The lethality against corn borers remains 100% even at a concentration of g / mL.

[0072] Experimental Example 6: Determination of the bioactivity of the target compound in controlling peach aphids indoors.

[0073] The target compound was dissolved in DMSO solution and diluted with TW-80 to obtain a stock solution with a concentration of 1 g / L. Subsequent dilutions with TW-80 yielded concentrations of 100.0, 10.0, and 1.0 g / L. μ Test solutions of g / mL and other concentrations were used. 40-50 peach aphids (2nd-3rd instar) were used to infect disposable small bowls of broad bean seedlings, and 2.5 mL of the test solution was sprayed on each seedling. A TW-80 solution containing DMSO was used as a blank control. Each group was repeated in triplicate. The treated peach aphids were reared in a greenhouse (temperature 26±2℃, humidity 85±5%, light / dark = 14 / 10h). The number of dead aphids was recorded after 48 hours. The mortality rate and corrected mortality rate were calculated as follows, and the activity data are shown in Table 7. Mortality rate = (Number of dead insects) / (Total number of insects treated) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 7. Insecticidal activity of compounds against peach aphids

[0074] Insecticidal activity results showed that compounds G2, G3, G4, G6, G8, G12, G14, G15, G16, G23, and G24 exhibited good insecticidal activity against peach aphids, with most compounds showing activity at 100 μL / min. μ At a concentration of g / mL, the mortality rate against peach aphids exceeded 80%, and compounds G4, G16, and G24 showed a mortality rate of over 80% at 10 g / mL. μ Even at a concentration of g / mL, the mortality rate against peach aphids remains 100%.

[0075] Experimental Example 7: Determination of the bioactivity of the target compound in controlling white-backed planthoppers indoors.

[0076] The target compound was dissolved in DMSO solution and diluted with TW-80 to obtain a stock solution with a concentration of 1 g / L. Subsequent dilutions with TW-80 yielded concentrations of 200.0, 100.0, and 10.0 g / L. μ Test solutions of g / mL and other concentrations were used. 40-50 white-backed planthoppers (2nd-3rd instar) were used to infect disposable small bowls of rice seedlings, and 2.5 mL of the test solution was sprayed on each. A TW-80 solution containing DMSO was used as a blank control. Each group was repeated in triplicate. The treated white-backed planthoppers were reared in a greenhouse (temperature 26±2℃, humidity 85±5%, light / dark = 14 / 10h). The number of dead planthoppers was recorded after 48 hours. The mortality rate and corrected mortality rate were calculated as follows, and the activity data are shown in Table 8. Mortality rate = (Number of dead insects) / (Total number of insects treated) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 8. Insecticidal activity of compounds against white-backed planthoppers

[0077] Insecticidal activity results showed that, among the compounds tested, compound G1 exhibited good insecticidal activity against the white-backed planthopper, while most compounds showed good activity at 100 mg / L. μ At a concentration of g / mL, compound G1 has a mortality rate exceeding 80% against white-backed planthoppers. μ The mortality rate against white-backed planthoppers remains 100% at a concentration of g / mL.

[0078] Furthermore, numerous tests have revealed that the compounds and their compositions described in this invention exhibit excellent control activity against many agricultural pests, including Lepidoptera (such as corn borers, cutworms, beet armyworms, cotton bollworms, fall armyworms, and armyworms), Homoptera (such as peach aphids, turnip aphids, pea aphids, peanut aphids, and broad bean aphids), and Hemiptera (such as brown planthoppers, white-backed planthoppers, and gray planthoppers). They are characterized by broad-spectrum activity, high efficiency, and rapid action, effectively controlling resistant pests and demonstrating promising application prospects.

Claims

1. A pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl cyano structure, characterized in that, Including compounds having the general formula [I] or their stereoisomers, N-oxides or their salts: Among them, Q1 and Q2 independently represent O or S respectively; X can represent C or N independently; R5 represents, independently, cyanoalkyl, halo- or unsubstituted pyrimidinyl, halo- or unsubstituted thiazolyl, or halo- or unsubstituted pyridinyl. R1-R4 are independently selected from at least one of hydrogen, tritium, alkyl, and halogen; R6 is selected from hydrogen, tritium, alkyl, halogen, alkoxy, haloalkoxy, and haloalkyl.

2. The pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl cyano structure according to claim 1, characterized in that: R5 represents cyanoalkyl, halo- or unsubstituted pyrimidinyl, halo- or unsubstituted thiazolyl, halo- or unsubstituted pyridinyl; R1-R4 are independently selected from at least one of hydrogen, tritium, C1-C8 alkyl, and halogen; R6 is selected from hydrogen, tritium, C1-C8 alkyl, halogen, C1-C8 alkoxy, halogenated C1-C8 alkoxy, and halogenated C1-C8 alkyl.

3. The pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl cyano structure according to claim 1, characterized in that: R5 represents cyanoalkyl, halo- or unsubstituted pyrimidinyl, halo- or unsubstituted thiazolyl, halo- or unsubstituted pyridinyl; R1-R4 are independently selected from at least one of hydrogen, tritium, C1-C6 alkyl, and halogen; R6 is selected from hydrogen, tritium, C1-C6 alkyl, halogen, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogenated C1-C6 alkyl.

4. A pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl cyano structure according to claim 1, characterized in that: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 5. A method for preparing a pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl cyano structure as described in any one of claims 1-3, comprising the following steps: The compound of general formula [II] is reacted with the compound of general formula [III] to prepare the compound of general formula [I]. The reaction equation is as follows: ； Wherein L1 and L2 represent halogens or -OH, -O-CH3, and -O-CH2CH3, respectively, and the definitions of substituents X, Q1, Q2, R1, R2, R3, R4, R5, and R6 are as described in any one of claims 1-3; Preferably, the reaction is carried out in the presence of a base and a solvent; more preferably, the base is selected from at least one inorganic or organic base, and the solvent is selected from at least one of DCM, diethyl ether, DMF, tetrahydrofuran, methyltetrahydrofuran, toluene, xylene, diphenyl ether, or dioxane.

6. A composition, characterized in that... The composition contains pyrido[1,2-a]pyrimidine metronid derivatives with an alkynyl cyano structure as described in any one of claims 1-4 and agriculturally usable adjuvants; the formulation of the composition is selected from emulsifiable concentrates (EC), powders (DP), wettable powders (WP), granules (GR), aqueous solutions (AS), suspensions (SC), ultra-low volume sprays (ULV), soluble powders (SP), microcapsules (MC), fumigants (FU), emulsions (EW), and water-dispersible granules (WG).

7. The use of the pyrido[1,2-a]pyrimidine metronid derivative containing an alkynyl cyano structure as described in any one of claims 1-4, or the composition of claim 6, in the preparation of a drug for controlling agricultural pests and diseases, wherein the agricultural pests and diseases are lepidopteran pests or hemiptera pests; wherein the agricultural pests are fall armyworm, beet armyworm, corn borer, cutworm, planthopper, and peach aphid.

8. A method for preventing and controlling agricultural pests and diseases, characterized in that: The pyrido[1,2-a]pyrimidine metronid derivative containing an alkynyl cyano structure as described in any one of claims 1-4, or the composition as described in claim 6, is applied to a harmful substance or its habitat; the agricultural pests are lepidopteran and hemiptera pests; the agricultural pests are fall armyworm, beet armyworm, corn borer, cutworm, planthopper, and peach aphid.

9. A method for protecting plants from agricultural pests and diseases, comprising the method step of contacting the pest with a pyrido[1,2-a]pyrimidine metronid derivative containing an alkynyl cyano structure as described in any one of claims 1-4, or the composition of claim 6.

10. An intermediate as described in formula 5[II].

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