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

Abstract

The invention relates to a pyrido [1, 2-a] pyrimidine mesoion derivative containing an alkynyl ferrocene structure as well as a preparation method and application of the pyrido [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, ostrinia nubilalis, cutworms, plant hoppers, aphis avenae and the like, and can be used for preparing drugs or medicaments for preventing and treating pests such as spodoptera frugiperda, ostrinia nubilalis, cutworms, sogatella furcifera, brown planthoppers, aphis avenae and the like. The structure and the preparation process are simple, and the production cost is low.

Description

Technical Field

[0001] This invention relates to the fields of chemical industry and pesticides, specifically to pyrido[1,2-a]pyrimidine metronidazole derivatives containing alkynyl ferrocene structure and their preparation methods, as well as the application of pyrido[1,2-a]pyrimidine metronidazole derivatives containing alkynyl ferrocene structure in the preparation of drugs for controlling fall armyworm, corn borer, cutworm, broad bean aphid, white-backed planthopper, and brown planthopper. Background Technology

[0002] In recent years, due to the long-term use of chemical pesticides, pest resistance has increased dramatically, leading to severe resistance to commonly used pesticides. For example, planthoppers and aphids (Hemiptera) and fall armyworms (Lepidoptera) are important pest groups in agricultural production and are also among the most resistant to pesticides.

[0003] Rice planthoppers (Nilaparvata lugens) are a persistent and devastating pest of rice crops in Asia. They disrupt rice growth by sucking phloem sap and laying eggs, and can also transmit plant viruses. In severely affected areas, if rice planthoppers are not controlled promptly and effectively, their combined damage can lead to large-scale yield reductions or even total crop failure in rice fields.

[0004] fall armyworm ( Spodoptera frugiperd The fall armyworm is a major pest of corn, rice, sorghum, sugarcane, peanuts, soybeans, and some non-food crops, such as cotton. It can reproduce year-round, making it a common pest. According to the Arthropod Pesticide Resistance Database (APRD), the fall armyworm has developed resistance to 47 insecticide active ingredients globally.

[0005] The cutworm (Agrotis ipsilon) is a major underground pest that damages seedlings of corn, cotton, sorghum, tobacco, wheat, sesame, beans, and various vegetables. Its damage is characterized by its stealth, voracious feeding, and devastating impact, often causing severe consequences such as missing seedlings and broken rows. It is one of the key pests requiring monitoring and control in agricultural production.

[0006] The Asian corn borer (Ostrinia furnacalis) is a borer that damages important crops such as corn, sorghum, millet, cotton, sugarcane, potatoes, and sunflowers, as well as various weeds. Its damage occurs throughout the entire growth cycle of corn. According to the Arthropod Resistance Database (APRD), globally, the corn borer has developed varying degrees of resistance to many insecticidal active ingredients, including organophosphates and pyrethroids.

[0007] The broad bean pruning aphid (Megoura japonica) is a significant piercing-sucking pest of leguminous crops such as broad beans, peas, alfalfa, and arrowhead peas. It can reproduce for multiple generations and remains active on its host plants even in winter. It directly damages plants by sucking sap, causing leaf curling, yellowing, growth point damage, and stunted growth. It can also indirectly cause damage by transmitting viral diseases; the broad bean pruning aphid is a key vector for leguminous viral diseases such as broad bean wilt virus. The losses caused by its virus transmission often far exceed the damage from its direct feeding. The characteristics of the broad bean pruning aphid's damage are "swarming and damaging young parts" and "efficient virus transmission." In agricultural production, a strategy of "controlling aphids to prevent diseases" is often adopted for its control.

[0008] In conclusion, there is an urgent need to develop insecticides with novel structures, high efficiency, low risk, and unique mechanisms of action.

[0009] 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.

[0010] 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.

[0011] Ferrocene derivatives possess various biological activities and applications in the pharmaceutical and chemical industries, such as anticancer activity, and chiral ferrocene phosphine ligands can be used in some transition element-catalyzed reactions. However, research reports on ferrocene and its derivatives in the pesticide field are relatively few, especially in the research of novel ferrocene derivatives with insecticidal activity.

[0012] In 2020, Huang Xiaobo et al. published an article in Industrial Crops and Products entitled "Renewableforest bioresources for pest management: Semisynthesis of esters containing ferrocene scaffolds of podophyllotoxin from Juniperus sabina L. as botanicalpesticides". The article reported eight podophyllotoxin ester derivatives containing ferrocene groups. The acaricidal activity showed that the introduction of ferrocene groups into the structure of podophyllotoxin ester derivatives was beneficial to improving their acaricidal activity. Among them, podophyllotoxin ester derivatives 11c and 11d, which contain ferrocene groups, showed the strongest potential insecticidal activity against Tetranychus cinnabarinus.

[0013] Based on the above research background, although thousands of patents have disclosed metronidicides and their biological activities, such as WO2011017342A2 and WO2021151034A1, the development of innovative, low-toxicity, and low-residue pest control agents with novel structures remains a key research focus both domestically and internationally. Therefore, this patent retains pyridine and [1,2- a Based on the active pyrimidine methanogenic framework, a class of pyrido[1,2-a]pyrimidine methanogenic derivatives containing an alkynyl ferrocene structure were designed and synthesized by introducing a ferrocene structure into the 3- or 4-position of the phenyl group. Bioassay results show that these compounds exhibit excellent insecticidal activity against lepidopteran pests such as fall armyworm, corn borer, and cutworm, as well as hemipteran pests such as broad bean aphid, white-backed planthopper, and brown planthopper, with a broad insecticidal spectrum. This provides new ideas and effective support for the development of novel insecticides. Summary of the Invention

[0014] 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 ferrocene structure and their preparation method. The compounds exhibit excellent control effects against pests such as fall armyworm, corn borer, cutworm, and white-backed planthopper.

[0015] Another object of the present invention is to provide a composition containing the above-mentioned derivatives.

[0016] Another object of the present invention is to provide the use of the above-described derivatives or compositions.

[0017] Another object of the present invention is to provide a method for controlling agricultural pests using the above-mentioned derivatives or compositions.

[0018] The technical solution adopted in this invention is as follows: In a first aspect, the present invention provides a pyrido[1,2-]pyridine-containing ferrocene 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; M represents Fe, Co, Ni, and Mg, respectively. R5 represents, independently, cyanoalkyl, halo- or unsubstituted pyrimidinyl, halo- or unsubstituted thiazolyl, or halo- 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 alkoxy, 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, substituted alkoxy, or substituted alkoxy is optionally substituted by at least one group selected from halogen, cycloalkyl, aryl, heterocyclic, ferrocene, -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.

[0019] In one specific embodiment, R5 represents cyanoC1-C8 alkyl, halo- or unsubstituted pyrimidinyl, halo- or unsubstituted thiazolyl, or halo- 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 C1-C8 alkoxy, 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, substituted C2-C8 alkynyl, or substituted C1-C8 alkoxy is optionally substituted by at least one group selected from halogen, C3-C8 cycloalkyl, aryl, heterocyclic, ferrocene, -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.

[0020] In another specific embodiment, R5 represents cyanoC1-C6 alkyl, halo- or unsubstituted pyrimidinyl, halo- or unsubstituted thiazolyl, halo- 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 C1-C6 alkoxy, 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, substituted C2-C6 alkynyl, or substituted C1-C6 alkoxy is optionally substituted by at least one group selected from halogen, C3-C6 cycloalkyl, aryl, heterocyclic, ferrocene, -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.

[0021] 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. Alkyl groups are, 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.

[0022] 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. , , , , , , , , , , , , , , , , , , , , , , , .

[0023] , , , , , 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 .

[0024] 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.

[0025] 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.

[0026] If various functional groups are present, the present invention also includes any ketone and enol tautomer forms, mixtures thereof, and salts thereof.

[0027] 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.

[0028] Secondly, another embodiment of this application is the pyrido[1,2-]pyridine containing the alkynyl ferrocene structure. 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.

[0029] 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 bases or organic bases. In one specific embodiment, the base is selected from at least one of inorganic bases (such as NaH, KH, NaOH, KOH, Na2CO3, K2CO3, Cs2CO3, KF, CsF) or organic bases (such as pyrazole, triethylamine, N,N-diisopropylethylamine, pyridine, DIEA, potassium trimethylsilanol, AcOK, AcONa, MeONa, EtONa, t-BuONa, t-BuOK, etc.).

[0030] 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.

[0031] The preparation methods of the compounds described in this invention can be found in WO2011017342A2, WO2021151034A1, etc.

[0032] The present invention also relates to an intermediate, as shown in formula [II] above.

[0033] Thirdly, the present invention also relates to the use of compounds of formula [I] or their stereoisomers, their N-oxides and salts, and compositions comprising them in the control of pests.

[0034] This invention provides a composition comprising pyrido[1,2-]pyridyl ferrocene containing an alkynyl 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).

[0035] 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.

[0036] This invention provides a method for controlling pests, the method comprising exposing the pest or its environment to a biologically effective amount of a compound of formula [I] or its stereoisomer, its N-oxide or its salt, or a combination thereof.

[0037] 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.

[0038] 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.

[0039] Solid compositions are generally available in the form of powders, granules, pellets, pellets, tablets, 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.

[0040] 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).

[0041] The compounds of the present invention can exist in the form of one or more stereoisomers. These 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.

[0042] 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.

[0043] Fifthly, the present invention provides pyrido[1,2-]pyridine containing the alkynyl ferrocene 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.

[0044] Preferably, the agricultural pests are fall armyworm, corn borer, cutworm, broad bean aphid, white-backed planthopper, and brown planthopper.

[0045] 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, corn borer, cutworm, broad bean aphid, white-backed planthopper, and brown planthopper.

[0046] 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-[1,2-]pyridine containing the alkynyl ferrocene structure. a Method steps for contacting pyrimidine mesonotropic derivatives or the composition described above.

[0047] The beneficial effects of this invention are: In this invention, the compounds have novel structures containing ferrocene with a chiral structure. 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, corn borer, cutworm, broad bean aphid, and rice planthopper. Some compounds show excellent insecticidal activity even at low doses (1... m Even under conditions of g / mL, it still exhibits high insecticidal activity. Therefore, the compound provided by this invention can improve the problem of high-dose application, fundamentally reducing the dosage and cost of application, and reducing 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.

[0048] 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.

[0049] Table 1. Compound structures and their HRMS (ESI) values

[0050] 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.

[0051] 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.

[0052] The specific synthesis steps of the representative compounds 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.

[0053] 1. Synthesis of compounds Example 1: Synthesis of Compound 1 (1) Add raw materials [1-2] (1.15 g, 5.49 mmol), cuprous iodide (99.50 mg, 522.45 μmol), and palladium dichloride bis(triphenylphosphine) (366.71 mg, 522.45 μmol) 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] (1.50 g, 5.22 mmol) (raw material [1-1] is prepared according to reference WO2024243693 A1) in 30 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 100 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 1.02 g of yellow solid [1-3], with a yield of 46.90%.

[0054] Fc= (2) The intermediate [1-3] (0.3 g, 522.45 μmol) and 10 mL of methanol were added to a 50 mL flask. At room temperature, 3 mL of NaOH (86.48 mg, 2.16 mmol) was dissolved and added dropwise to the reaction system. The reaction was carried out overnight at room temperature. After the reaction was completed, 50 mL of water was added to dilute the solution. The solution was extracted once with 20 mL of ethyl acetate. The solution was adjusted to acidity with dilute hydrochloric acid to pH 1-2. The solution was then extracted three times with 20 mL 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 0.25 g of white solid [1-4], with a yield of 89.36%.

[0055] (3) Add intermediate [1-4] (0.25 g, 644.00 μmol) to a 50 mL flask, add 15 mL DCM and catalytic amount of DMF to a round bottom flask, add oxalyl chloride (0.41 g, 3.22 mmol) dropwise under ice bath, and after the reaction is completed in 2 h, remove the solvent under reduced pressure, add 20 mL of dichloromethane for later use, dissolve intermediate [1-5] (0.15 g, 666.92 μmol) and base TEA (64.27 mg, 635.17 μmol) in 10 mL DCM, mix well and add dropwise to the reaction system at 0 °C, after the reaction is about 30 min, add 1 mL of methanol to quench the reaction, add silica gel to stir the sample, separate the target product by chromatography column, and slurry with ethyl acetate and petroleum ether to obtain 82 mg of yellow solid [1], with a yield of 22.34%.

[0056] Example 2: Synthesis of Compound 2 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: Synthesis of Compound 3 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: Synthesis of Compound 4 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 3-(2-pyridylamino)propionitrile (prepared in reference WO2018105492 A1). Example 5: Synthesis of Compound 5 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 6: Synthesis of Compound 6 Consistent with Example 1, except that in step (1), intermediate [1-1] is replaced with ; Steps (2) to (3) are the same as steps (2) to (3) in Example 1; Examples 7-10: Synthesis of Compound 7-10 Steps (1) to (3) are the same as steps (1) to (3) in Example 6, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0057] Example 11: Synthesis of Compound 11 Consistent with Example 1, except that in step (1), intermediate [1-1] is replaced with .

[0058] Examples 12-15: Synthesis of Compounds 12-15 Steps (1) to (3) are the same as steps (1) to (3) in Example 11, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0059] Example 16: Synthesis of Compound 16 Consistent with Example 1, except that in step (1), intermediate [1-1] is replaced with .

[0060] Example 17: Synthesis of compounds 17-20 Steps (1) to (3) are the same as steps (1) to (3) in Example 16, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0061] Example 21: Synthesis of Compound 21 Consistent with Example 1, except that in step (1), intermediate [1-1] is replaced with .

[0062] Examples 22-25: Synthesis of compounds 22-25 Steps (1) to (3) are the same as steps (1) to (3) in Example 21, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0063] Example 26: Synthesis of Compound 26 Consistent with Example 1, except that in step (1), intermediate [1-1] is replaced with .

[0064] Examples 27-30: Synthesis of compounds 27-30 Steps (1) to (3) are the same as steps (1) to (3) in Example 26, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0065] Example 31: Synthesis of Compound 31 Consistent with Example 1, except that in step (1), intermediate [1-1] is replaced with .

[0066] Examples 32-35: Synthesis of compounds 32-35 Steps (1) to (3) are the same as steps (1) to (3) in Example 31, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0067] Example 36: Synthesis of Compound 36 Consistent with Example 1, except that in step (1), intermediate [1-1] is replaced with .

[0068] Examples 37-40: Synthesis of compounds 37-40 Steps (1) to (3) are the same as steps (1) to (3) in Example 36, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5, respectively.

[0069] Example 41: Synthesis of Compound 41 Steps (1) to (3) are the same as steps (1) to (3) in Example 1, wherein the Fe in the ferrocene-based intermediate [1-2] is modified to Co.

[0070] Examples 42-45: Synthesis of compounds 42-45 Steps (1) to (3) are the same as steps (1) to (3) in Example 41, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0071] Example 46: Synthesis of Compound 46 Steps (1) to (3) are the same as steps (1) to (3) in Example 1, wherein the Fe in the ferrocene-based intermediate [1-2] is modified to Ni.

[0072] Examples 47-50: Synthesis of compounds 47-50 Steps (1) to (3) are the same as steps (1) to (3) in Example 46, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0073] Example 51: Synthesis of Compound 51 Steps (1) to (3) are the same as steps (1) to (3) in Example 1, wherein the Fe of the ferrocene group in intermediate [1-2] is modified to Mg.

[0074] Implementation 52-55: Synthesis of compounds 52-55 Steps (1) to (3) are the same as steps (1) to (3) in Example 51, wherein intermediates [1-5] are the same as in Example 2, Example 3, Example 4 and Example 5 respectively.

[0075] 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 (such as fall armyworm, corn borer, cutworm, white-backed planthopper, brown planthopper, and broad bean aphid) were selected and placed in disposable transparent boxes. Each box contained 10 (Lepidoptera) / 40 (Hemiptera) insects of similar growth, along with host plant leaves (corn leaves, lotus leaves, rice seedlings, and 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.

[0076] 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).

[0077] Insecticidal activity results showed that compound 5 had good insecticidal activity against fall armyworm, with most compounds showing activity at 200 μL / min. m Compound 5 showed a 100% lethality against fall armyworm at a concentration of g / mL, and at 10 g / mL... m The mortality rate against fall armyworm remains 100% at a concentration of g / mL.

[0078] "-" indicates no data; positive controls: trifluoropyrimidine and dichloropyrimidine.

[0079] Example 2: Indoor bioactivity assay of target compound for controlling corn borer.

[0080] 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 3. Mortality Rate = (Number of Dead Insects) / (Total Number of Treated Insects) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 3. Insecticidal activity of the compounds in the examples against corn borers

[0081] Insecticidal activity results showed that compound 5 had good insecticidal activity against the corn borer, with most compounds showing activity at 200 μL / min. m Compound 5 had a lethality of 100% against corn borers at a concentration of g / mL, and at 10 g / mL... m The lethality against corn borers remains 100% even at a concentration of g / mL.

[0082] "-" indicates no data; positive controls: trifluoropyrimidine and dichloropyrimidine.

[0083] Example 3 of biological test: Determination of the bioactivity of the target compound in controlling cutworms indoors.

[0084] Second-instar cutworms of uniform physiological condition were selected for testing. Ten cutworms were picked from each culture dish and placed in disposable transparent boxes. Ten second-instar corn borers of uniform growth were also placed in each box, along with host plant leaves (corn leaves). The mixture was then sprayed using a spray tower. After spraying, the lid was tightly closed. This process was repeated three times. The highest dose of DMSO solution was used as a control. After treatment, the cutworms 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 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 cutworms

[0085] Insecticidal activity results showed that compound 5 had good insecticidal activity against cutworms, and compound 5 showed good insecticidal activity at 10... m The lethality against corn borers remains 100% even at a concentration of g / mL.

[0086] "-" indicates no data; positive controls: trifluoropyrimidine and dichloropyrimidine.

[0087] Experimental Example 4: Determination of the bioactivity of the target compound in controlling broad bean aphids in the room.

[0088] 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. m Test solutions of g / mL and other concentrations were used. 30-40 broad bean aphids (2nd-3rd instar) were used to infect broad bean seedlings in flowerpots, and 2 mL of test solution was sprayed on top. A TW-80 solution containing DMSO was used as a blank control. Each group was repeated in triplicate. The treated broad bean 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 lethality rate and corrected lethality rate were calculated as follows, and the activity data are shown in Table 5. Mortality rate = (Number of dead insects) / (Total number of insects treated) × 100 Corrected lethality = (treatment lethality - blank lethality) / (1 - blank lethality) × 100 Table 5. Insecticidal activity of compounds against broad bean aphids.

[0089] Insecticidal activity results showed that compound 5 had good insecticidal activity against broad bean aphids, with most compounds showing activity at 100 μL / min. m At a concentration of g / mL, compound 5 had a mortality rate of 100% against the broad bean aphid. m Even at a concentration of g / mL, the mortality rate against broad bean aphids remained at 100%.

[0090] "-" indicates no data; positive controls: trifluoropyrimidine and dichloropyrimidine.

[0091] Experimental Example 5: Determination of the bioactivity of the target compound in controlling white-backed planthoppers indoors.

[0092] 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. m 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 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 compounds against white-backed planthoppers

[0093] Insecticidal activity results showed that compound 3 had good insecticidal activity against the white-backed planthopper, with most compounds showing activity at 100 μL / min. m At a concentration of g / mL, compound 3 showed a mortality rate exceeding 75% against the white-backed planthopper. m The mortality rate against white-backed planthoppers remains 100% at a concentration of g / mL.

[0094] Positive controls: trifluoropyrimidine and dichlorothiapyrimidine.

[0095] Experimental Example 6: Determination of the bioactivity of the target compound in controlling brown planthoppers indoors.

[0096] 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. mTest solutions of g / mL and other concentrations were used. 40-50 brown 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 brown 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 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 brown planthoppers

[0097] Insecticidal activity results showed that compound 3 had good insecticidal activity against the white-backed planthopper, with most compounds showing activity at 100 μL / min. m At a concentration of g / mL, compound 3 showed a mortality rate exceeding 75% against the white-backed planthopper. m The mortality rate against white-backed planthoppers remains 100% at a concentration of g / mL.

[0098] Positive controls: trifluoropyrimidine and dichlorothiapyrimidine.

[0099] 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, and peanut aphids), and Hemiptera (such as brown planthoppers, white-backed planthoppers, and gray planthoppers). They possess broad-spectrum, high-efficiency, and systemic properties, effectively controlling resistant pests and demonstrating promising application prospects.

Claims

1. A pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl ferrocene structure as shown in general formula [I], 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; M represents Fe, Co, Ni, and Mg, respectively. 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, haloalkyl, and halogen; R6 is selected from hydrogen, tritium, alkyl, halogen, alkoxy, haloalkoxy, haloalkyl, alkynyl group substituted with or unsubstituted with at least one of ferrocene group or cycloalkyl group.

2. The pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl ferrocene structure according to claim 1, characterized in that: R5 represents cyano C1-C8 alkyl, 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, haloalkyl, and halogen; R6 is selected from hydrogen, tritium, C1-C8 alkyl, halogen, C1-C8 alkoxy, halo-C1-C8 alkoxy, halo-C1-C8 alkyl, alkynyl group substituted with or unsubstituted by at least one of ferrocene group or C3-C8 cycloalkyl. 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.

3. The pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl ferrocene structure according to claim 1, characterized in that: R5 represents cyanoC1-C6 alkyl, 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, haloalkyl, and halogen; R6 is selected from hydrogen, tritium, C1-C6 alkyl, halogen, C1-C6 alkoxy, halogenated C1-C6 alkoxy, halogenated C1-C6 alkyl, alkynyl group substituted with or unsubstituted by at least one of ferrocene group or C3-C6 cycloalkyl.

4. The pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl ferrocene structure according to claim 1, characterized in that: Compound 1: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Fe; Compound 2: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Fe; Compound 3: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Fe; Compound 4: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Fe; Compound 5: R1=H, R2=H, R3=H, R4=CH3, R5= , R6=H, Q1=O, Q2=O, X=C, M=Fe; Compound 6: R1=H, R2=H, R3=H, R4=H, R5= , R6=CH3, Q1=O, Q2=O, X=C, M=Fe; Compound 7: R1=H, R2=H, R3=H, R4=H, R5= , R6=CH3, Q1=O, Q2=O, X=C, M=Fe; Compound 8: R1=H, R2=H, R3=H, R4=H, R5= , R6=CH3, Q1=O, Q2=O, X=C, M=Fe; Compound 9: R1=H, R2=H, R3=H, R4=H, R5= , R6=CH3, Q1=O, Q2=O, X=C, M=Fe; Compound 10: R1=H, R2=H, R3=H, R4=CH3, R5= , R6=CH3, Q1=O, Q2=O, X=C, M=Fe; Compound 11: R1=H, R2=H, R3=H, R4=H, R5= , R6=Cl, Q1=O, Q2=O, X=C, M=Fe; Compound 12: R1=H, R2=H, R3=H, R4=H, R5= , R6=Cl, Q1=O, Q2=O, X=C, M=Fe; Compound 13: R1=H, R2=H, R3=H, R4=H, R5= , R6=Cl, Q1=O, Q2=O, X=C, M=Fe; Compound 14: R1=H, R2=H, R3=H, R4=H, R5= , R6=Cl, Q1=O, Q2=O, X=C, M=Fe; Compound 15: R1=H, R2=H, R3=H, R4=CH3, R5= , R6=Cl, Q1=O, Q2=O, X=C, M=Fe; Compound 16: R1=H, R2=H, R3=H, R4=H, R5= , R6=OCF3, Q1=O, Q2=O, X=C, M=Fe; Compound 17: R1=H, R2=H, R3=H, R4=H, R5= , R6=OCF3, Q1=O, Q2=O, X=C, M=Fe; Compound 18: R1=H, R2=H, R3=H, R4=H, R5= , R6=OCF3, Q1=O, Q2=O, X=C, M=Fe; Compound 19: R1=H, R2=H, R3=H, R4=H, R5= , R6=OCF3, Q1=O, Q2=O, X=C, M=Fe; Compound 20: R1=H, R2=H, R3=H, R4=CH3, R5= , R6=OCF3, Q1=O, Q2=O, X=C, M=Fe; Compound 21: R1=H, R2=H, R3=H, R4=H, R5= , R6=OCH3, Q1=O, Q2=O, X=C, M=Fe; Compound 22: R1=H, R2=H, R3=H, R4=H, R5= , R6=OCH3, Q1=O, Q2=O, X=C, M=Fe; Compound 23: R1=H, R2=H, R3=H, R4=H, R5= , R6=OCH3, Q1=O, Q2=O, X=C, M=Fe; Compound 24: R1=H, R2=H, R3=H, R4=H, R5= , R6=OCH3, Q1=O, Q2=O, X=C, M=Fe; Compound 25: R1=H, R2=H, R3=H, R4=CH3, R5= , R6=OCH3, Q1=O, Q2=O, X=C, M=Fe; Compound 26: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 27: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 28: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 29: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 30: R1=H, R2=H, R3=H, R4=CH3, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 31: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 32: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 33: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 34: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 35: R1=H, R2=H, R3=H, R4=CH3, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 36: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 37: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 38: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 39: R1=H, R2=H, R3=H, R4=H, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 40: R1=H, R2=H, R3=H, R4=CH3, R5= R6= , Q1=O, Q2=O, X=C, M=Fe; Compound 41: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Co; Compound 42: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Co; Compound 43: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Co; Compound 44: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Co; Compound 45: R1=H, R2=H, R3=H, R4=CH3, R5= , R6=H, Q1=O, Q2=O, X=C, M=Co; Compound 46: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Ni; Compound 47: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Ni; Compound 48: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Ni; Compound 49: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Ni; Compound 50: R1=H, R2=H, R3=H, R4=CH3, R5= , R6=H, Q1=O, Q2=O, X=C, M=Ni; Compound 51: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Mg; Compound 52: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Mg; Compound 53: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Mg; Compound 54: R1=H, R2=H, R3=H, R4=H, R5= , R6=H, Q1=O, Q2=O, X=C, M=Mg; Compound 55: R1=H, R2=H, R3=H, R4=CH3, R5= , R6=H, Q1=O, Q2=O, X=C, M=Mg.

5. A method for preparing a pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl ferrocene structure as described in any one of claims 1-4, 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, M, 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 metronidide derivatives with an alkynyl ferrocene 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 mesonotropic derivative containing an alkynyl ferrocene 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 are fall armyworm, corn borer, cutworm, broad bean aphid, white-backed planthopper, and brown planthopper.

8. A method for preventing and controlling agricultural pests and diseases, characterized in that: The pyrido[1,2-a]pyrimidine mesonotropic derivative containing an alkynyl ferrocene structure as described in any one of claims 1-4, or the composition as described in claim 6, is applied to the harmful substance or its habitat; the agricultural pest is fall armyworm, corn borer, cutworm, broad bean aphid, white-backed planthopper, and brown planthopper.

9. A method for protecting plants from agricultural pests and diseases, comprising the step of contacting the pest with a pyrido[1,2-a]pyrimidine metronidium derivative containing an alkynyl ferrocene 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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