Use of butachlor analogs and plant pest control composition containing the same

Abstract

The present application belongs to the technical field of plant disease and pest control, and particularly relates to the use of a dinobuton analogue and a plant pest control composition containing the same. According to the natural plant source compound dinobuton with insecticidal activity, on the basis of the natural dinobuton parent structure, amino, methoxy and bromine substituent groups are introduced into the benzene ring, and the ring structure of the heterocycle and the position of the carbonyl group are differentially modified, thereby obtaining multiple dinobuton analogues with good insecticidal activity on hemipteran, thysanopteran and dipteran pests. Surprisingly, the toxicity of 6-amino-2H-1,4-benzoxazin-3(4H)-one to the small brown planthopper is 1.86 times that of the parent dinobuton, and it has the characteristics of low toxicity and high efficiency, thereby laying a foundation for the research and development of a new type of plant source insecticidal preparation.

Description

Technical Field

[0001] This invention belongs to the field of plant disease and pest control technology, particularly in the field of research and development of plant-derived insecticidal compounds and green control technology of crop pests, specifically involving the use of butylated ... Background Technology

[0002] In agricultural ecosystems, chemical pesticides remain the fastest and most effective means of controlling pest outbreaks. However, with long-term and single-use, the increasing resistance of pests and their resurgence are becoming more prominent problems, seriously threatening crop production safety. Plant-derived pesticides have received widespread attention due to their natural origin and safety; however, the insecticidal activity of plant-derived compounds is generally significantly lower than that of chemical pesticides, which has become a core bottleneck for their reliable field application.

[0003] Dingbu ( Figure 1 Iron(III) ions (IVI) are a naturally derived defense substance in the chemical defense system of grasses such as maize, wheat, and rye. They exhibit strong free radical scavenging activity and relatively weak iron(III) ion reducing activity, possessing antioxidant activity and growth-inhibiting properties against many studied bacterial and fungal strains. However, research on the insecticidal activity of IVI and its structural analogs is still very limited. Therefore, screening for IVI structural analogs with significant insecticidal activity is of great significance for promoting the practical application of plant-derived insecticides. Summary of the Invention

[0004] Therefore, the present invention aims to disclose a new approach for the research and development of plant-derived insecticidal compounds and the green control of crop pests.

[0005] To achieve the above objectives, the present invention aims to provide the use of a butylated phthalate analogue in the control of plant pests. The following technical solution is adopted:

[0006] The use of butazoline analogues in the control of plant pests, wherein the butazoline analogues include 6-amino-2H-1,4-benzoxazine-3(4H)-one, 6-methoxybenzoxazine-2(3H)-one, 2H-1,4-benzoxazine-3(4H)-one, 6-bromo-2H-1,4-benzoxazine-3(4H)-one, 7-bromo-2H-1,4-benzoxazine-3(4H)-one, 7-methoxy-2H-benzo[b][1,4]oxazine-3(4H)-one, 6-bromo-3,4-dihydro-2H-benzo[1,4]oxazine, or 7-bromo-3,4-dihydro-2H-1,4-benzoxazine.

[0007] It is worth noting that existing research shows that single-dimensional modification (benzene ring substitution only or heterocyclic carbonyl modification only) is insufficient to significantly enhance insecticidal activity. Only when specific substituents on the benzene ring synergistically interact with specific heterocyclic and carbonyl arrangements can the derivatives possess high insecticidal activity. The butyl analogs disclosed in this invention, based on the natural butyl parent structure, introduce amino, methoxy, and bromine substituents into the benzene ring, while simultaneously modifying the ring structure and carbonyl position of the heterocyclic ring. This allows the butyl analogs to exhibit insecticidal activity against multiple groups of pests, including Hemiptera, Thysanoptera, and Diptera, significantly broadening the target range for butyl compounds.

[0008] Furthermore, the butyl analogues include 6-amino-2H-1,4-benzoxazine-3(4H)-one or 7-methoxy-2H-benzo[b][1,4]oxazine-3(4H)-one.

[0009] Furthermore, the plant pests include hemiptera, thalassoptera, and dipteran pests.

[0010] Furthermore, the plant pests include planthoppers, peach aphids, peanut aphids, tobacco whiteflies, western flower thrips, or citrus fruit flies.

[0011] Furthermore, applicable plants include food crops, vegetable crops, fruit trees, cash crops, ornamental crops, and medicinal crops.

[0012] It is worth noting that for those skilled in the art, it is difficult to predict the impact of structural modifications on insecticidal activity based solely on existing structure-activity relationship experience: even minor group substitutions or site modifications at the molecular level can lead to a sharp decline or even complete loss of insecticidal activity, making it difficult to achieve the rational and targeted design of highly active derivatives. Typically, it is necessary to synthesize and screen candidate compounds in large quantities, but most butyric acid analogues fail to achieve a significant improvement in insecticidal activity. Therefore, there is no predictable structure-activity relationship between the chemical structure of butyric acid derivatives and their insecticidal activity, which poses a significant obstacle to the development of highly active butyric acid insecticidal lead compounds. This invention, however, overcomes the aforementioned technical barriers at the screening level by achieving synergistic effects between specific substituents on the benzene ring and specific heterocycles and carbonyl arrangements, obtaining target derivatives with significantly superior activity to the parent butyric acid. It also effectively broadens the target range of butyric acid compounds, laying an important foundation for the practical application of plant-derived insecticides.

[0013] The second objective of this invention is to provide a plant pest control composition.

[0014] A plant pest control composition comprising a butyl analogue and an adjuvant.

[0015] It is worth noting that the adjuvant is one or more of the following: wetting agent, dispersant, emulsifier, solvent, cosolvent, thickener, stabilizer, antifreeze, defoamer, preservative, binder, wall material, acid-adjusting medium, alkali-adjusting medium, and solid inert carrier. In this invention, there are no special requirements for the adjuvant; commonly used components in the art can be selected as needed. These components can be used in conventional amounts according to the formulation of existing pesticide compositions, which is well known to those skilled in the art and will not be elaborated further here.

[0016] Furthermore, the butyl analogues include 6-amino-2H-1,4-benzoxazine-3(4H)-one, 6-methoxybenzoxazine-2(3H)-one, 2H-1,4-benzoxazine-3(4H)-one, 6-bromo-2H-1,4-benzoxazine-3(4H)-one, 7-bromo-2H-1,4-benzoxazine-3(4H)-one, 7-methoxy-2H-benzo[b][1,4]oxazine-3(4H)-one, 6-bromo-3,4-dihydro-2H-benzo[1,4]oxazine, or 7-bromo-3,4-dihydro-2H-1,4-benzoxazine.

[0017] Furthermore, the dosage form of the composition includes solid dosage forms, liquid dosage forms, and special dosage forms.

[0018] In this invention, the solid dosage form is optionally selected from powder (DP), wettable powder (WP), soluble powder (SP), granules (GR), water-dispersible granules (WG), tablets (PT), and fumigants (FU); the liquid dosage form is optionally selected from emulsifiable concentrate (EC), emulsion (EW), microemulsion (ME), suspension concentrate (SC), suspension concentrate (SE), aqueous solution (AS), and oil (OL); the special dosage form is optionally selected from seed coating agent (FS), corrosion inhibitor (CR), ultra-low volume spray (ULV), and paste (PA).

[0019] Compared with existing technologies, this invention, based on the insecticidal natural plant-derived compound butyl, introduces amino, methoxy, and bromine substituents into the benzene ring according to the structure of the natural butyl parent compound. Simultaneously, it differentiates the ring structure and carbonyl position of the heterocycle, resulting in several butyl analogs with good insecticidal activity against Hemiptera, Thysanoptera, and Diptera pests. Surprisingly, 6-amino-2H-1,4-benzoxazine-3(4H)-one exhibits 1.86 times the toxicity against the planthopper butyl parent compound, demonstrating low toxicity and high efficiency, laying the foundation for the development of novel plant-derived insecticides. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0021] Figure 1 It is a ductile fabric structure.

[0022] Figure 2 The structural formulas of the eight butyl analogues disclosed in this invention are shown below. Detailed Implementation

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.

[0025] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0026] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.

[0027] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.

[0028] The present invention proposes the use of DIMBOA analogs and a plant pest control composition containing the same, belonging to the technical field of plant disease and pest control. According to DIMBOA, a natural plant-derived compound with insecticidal activity, the present invention introduces amino, methoxy and bromine substituent groups into the benzene ring on the basis of the parent structure of natural DIMBOA, and carries out differentiated modification on the ring structure of the heterocycle and the position of the carbonyl group, so as to obtain a plurality of DIMBOA analogs with good insecticidal activity against pests of Hemiptera, Thysanoptera and Diptera. Unexpectedly, the virulence of 6-amino-2H-1,4-benzoxazin-3(4H)-one to Laodelphax striatellus is 1.86 times that of the parent DIMBOA, which has the characteristics of low toxicity and high efficiency, and lays a foundation for the research and development of new plant-derived insecticidal formulations.

[0029] For a better understanding of the present invention, the present invention is further specifically illustrated through the following examples, which should not be construed as a limitation to the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above disclosure of the present invention shall also be regarded as falling within the protection scope of the present invention.

[0030] Example 1 Laodelphax striatellus was reared in the light incubator of this laboratory (temperature 25±1℃, humidity 70-80%, 16 h light / 8 h dark), and 3rd-instar Laodelphax striatellus was selected as the test insect for virulence determination; the virulence was determined by the topical application method, and the instrument used was SMARTouch™ Controller for UMP3 (World Precision Instruments LLC, USA); DIMBOA ( Figure 1 ) and 8 structurally similar compounds ( Figure 2 ) were dissolved in dimethyl sulfoxide (DMSO); each compound was diluted into 5 concentration gradients with acetone, 0.05 μL of the agent was topically applied to the pronotum of Laodelphax striatellus using a topical applicator, and Laodelphax striatellus topically applied with 0.05 μL of acetone was used as the control; each treatment contained 25 Laodelphax striatellus, with three biological replicates; the mortality rate was checked 72 h after treatment.

[0031] Among them, compound 1: 6-amino-2H-1,4-benzoxazine-3(4H)-one (CAS No. 89976-75-0), compound 2: 6-methoxybenzoxazole-2(3H)-one (CAS No. 532-91-2), compound 3: 2H-1,4-benzoxazine-3(4H)-one (CAS No. 5466-88-6), compound 4: 6-bromo-2H-1,4-benzoxazine-3(4H)-one (CAS No. 24036-52-0), compound 5: 7- Bromo-2H-1,4-benzoxazine-3(4H)-one (CAS No. 321436-06-0), Compound 6: 7-methoxy-2H-benzo[b][1,4]oxazine-3(4H)-one (CAS No. 6529-94-8), Compound 7: 6-bromo-3,4-dihydro-2H-benzo[1,4]oxazine (CAS No. 105655-01-4), Compound 8: 7-bromo-3,4-dihydro-2H-1,4-benzooxazine (CAS No. 105679-22-9).

[0032] Table 1. Toxicity determination of butylated tinib and its structurally similar compounds

[0033] Table 1 shows that butylated oxalis itself has high insecticidal activity against planthoppers. Eight compounds with similar structures to butylated oxalis all showed some insecticidal effect against planthoppers. Among them, 6-amino-2H-1,4-benzoxazine-3(4H)-one showed the highest insecticidal activity against planthoppers, 1.86 times that of the parent compound butylated oxalis. 7-methoxy-2H-benzo[b][1,4]oxazine-3(4H)-one showed comparable insecticidal activity against planthoppers to the parent compound butylated oxalis.

[0034] Example 2 The tested pests, peach aphid, peanut aphid, tobacco whitefly, western flower thrips, and citrus fruit fly, were reared in light incubators under the following conditions: temperature 25 ± 1 ℃, humidity 70 – 80%, light exposure 16 h / dark exposure 8 h.

[0035] Toxicity assay test insects: adult insects. Toxicity was determined using the drop method, and the instrument was a SMARTouch™ Controller for UMP3 (World Precision Instruments LLC, USA).

[0036] 6-Amino-2H-1,4-benzoxazine-3(4H)-one was dissolved in dimethyl sulfoxide (DMSO). The compound was diluted with acetone to five concentration gradients. 0.05 μL of the solution was applied dropwise to the back of the test insects using a dropper. Insects treated with 0.05 μL of acetone served as controls. Each treatment contained 25 insects, with three biological replicates. Mortality was assessed after 72 h of treatment.

[0037] Table 2. Insecticidal spectrum of 6-amino-2H-1,4-benzoxazine-3(4H)-one

[0038] Table 2 shows that the 6-amino-2H-1,4-benzoxazine-3(4H)-one, a structural analog of butylidene, exhibits good insecticidal activity against hemiptera pests such as peach aphid, peanut aphid, and whitefly; tsamptera pests such as western flower thrips; and dipteran pests such as oriental fruit fly. Among these, the insecticidal activity is particularly high against the hemiptera pest whitefly and the tsamptera pest western flower thrips.

[0039] Therefore, the butyl analogues obtained by this invention exhibit insecticidal activity against multiple groups of pests, including Hemiptera, Thysanoptera, and Diptera, significantly broadening the target range of butyl compounds. This effectively solves the problem that most existing butyl and its derivatives are only effective against a few pests, and that butyl plant-derived insecticides have a narrow target range.

[0040] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. The use of butylated phthalate analogues in the control of plant pests, characterized in that, The butylidene analogues include 6-amino-2H-1,4-benzoxazine-3(4H)-one, 6-methoxybenzoxazine-2(3H)-one, 2H-1,4-benzoxazine-3(4H)-one, 6-bromo-2H-1,4-benzoxazine-3(4H)-one, 7-bromo-2H-1,4-benzoxazine-3(4H)-one, 7-methoxy-2H-benzo[b][1,4]oxazine-3(4H)-one, 6-bromo-3,4-dihydro-2H-benzo[1,4]oxazine, or 7-bromo-3,4-dihydro-2H-1,4-benzoxazine.

2. The use of the butadiene analogue according to claim 1 in the control of plant pests, characterized in that, The butyl analogues include 6-amino-2H-1,4-benzoxazine-3(4H)-one or 7-methoxy-2H-benzo[b][1,4]oxazine-3(4H)-one.

3. The use of the butadiene analogue according to claim 1 in the control of plant pests, characterized in that, The plant pests include hemiptera, thalassoptera, and dipteran pests.

4. The use of the butadiene analogue according to claim 3 in the control of plant pests, characterized in that, The plant pests mentioned include planthoppers, peach aphids, peanut aphids, tobacco whiteflies, western flower thrips, or citrus fruit flies.

5. The use of the butadiene analogue according to claim 1 in the control of plant pests, characterized in that, Applicable plants include food crops, vegetable crops, fruit trees, cash crops, ornamental crops, and medicinal crops.

6. A plant pest control composition, characterized in that, It contains the butyl analogue and additives as described in claim 1.

7. The plant pest control composition according to claim 6, characterized in that, The butylidene analogues include 6-amino-2H-1,4-benzoxazine-3(4H)-one, 6-methoxybenzoxazine-2(3H)-one, 2H-1,4-benzoxazine-3(4H)-one, 6-bromo-2H-1,4-benzoxazine-3(4H)-one, 7-bromo-2H-1,4-benzoxazine-3(4H)-one, 7-methoxy-2H-benzo[b][1,4]oxazine-3(4H)-one, 6-bromo-3,4-dihydro-2H-benzo[1,4]oxazine, or 7-bromo-3,4-dihydro-2H-1,4-benzoxazine.

8. The plant pest control composition according to claim 6, characterized in that, The dosage forms of the composition include solid dosage forms, liquid dosage forms, and special dosage forms.

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