Composition biologically active against stenoma catenifer, and sustained release preparation for control use containing the same

Abstract

To provide a composition or the like by which the number of attraction becomes larger than (9Z)-9,13-tetradecadiene-11-ynal alone.SOLUTION: Provided are a composition biologically active against Stenoma catenifer(STENCA) containing at least (9Z)-9,13-tetradecadiene-11-ynal (1) and (9E)-9,13-tetradecadiene-11-ynal (2), a sustained release preparation for controlling STENCA which comprises the composition and a carrier or a container for releasing the (9Z)-9,13-tetradecadiene-11-ynal (1) and (9E)-9,13- tetradecadiene-11-ynal (2) in a controlled manner, and a method for controlling STENCA including at least a step of installing the sustained release preparation in a farm field and releasing the (9Z)-9,13-tetradecadiene-11-ynal (1) and (9E)-9,13-tetradecadiene-11-ynal (2) into the farm field.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to Stenoma catenifer The present invention relates to a composition that is physiologically active against and a sustained-release formulation for control containing the same. [Background technology]

[0002] Avocado seed moth (scientific name: Stenoma catenifer (hereinafter referred to as the scientific name) is the most important pest of avocados in Latin America, including Mexico, Guatemala, Peru, Ecuador, and Brazil, and is a major problem because it directly attacks the fruit. For example, in some areas of South America, pesticides are sprayed 7 to 11 times a season, but it is said that 60% of the fruit is still damaged. One of the reasons for this is that the larvae of this pest penetrate into the flesh of the fruit, making it difficult to control with insecticides. For these reasons, biological control methods are gaining attention, and one promising method is the use of sex pheromones.

[0003] Control methods that use sex pheromone substances include mass trapping or attract and kill, which uses a pheromone attractant to attract adult insects, gather them in a certain place, and capture (kill) them to reduce the pest density in the field; push-pull, which uses a pheromone attractant and a repellent to move pests in a certain direction and capture (kill) them to reduce the pest density in the field; attract and infect, which uses a pheromone attractant to attract adult insects, infects them with pathogens, and releases them into the field to infect the target pests with the pathogens in the field, thereby reducing the pest density of the next generation; and mating disruption, which uses a pheromone agent to prevent them from finding a mating partner in the field, thereby reducing the pest density of the next generation (Non-Patent Document 1). In any of the above control methods, an attractant composition capable of attracting a large number of target pests with high accuracy is important.

[0004] Stenoma catenifer It has been reported that the sex pheromone of this insect is (9Z)-9,13-tetradecadien-11-ynal (Non-Patent Documents 2 and 3). [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] BSHansson (Ed.), Insect Olfaction, Chapter 12 “Applied Aspects of Insect Olfaction”, 352-377. [Non-Patent Document 2] Jocelyn G. Millar et al,2008,Tetrahedron Letters.49:4820-4823. [Non-Patent Document 3] Mark S. Hoddle et al,2009,J.Econ.Entomol.,102(4):1460-1467. [Non-Patent Document 4] Aivle Cabrera, J.Chem.Ecol.,2001,27(10),2097. Summary of the Invention [Problem to be solved by the invention]

[0006] However, according to Non-Patent Document 3, among the many attractant compositions used in field tests, a composition containing only (9Z)-9,13-tetradecadien-11-ynal as a physiologically active ingredient was the most active, and although attractant activity against males was confirmed, as the authors acknowledge, the amount of attractant itself was small, and the attractant activity was not sufficient. For this reason, in order to put the attractant composition into practical use, Stenoma catenifer Considering the severity of the agricultural damage caused by these insects, there has been a strong desire for an attractant composition that is even slightly more active than existing compositions. The present invention has been made in consideration of the above circumstances, and aims to provide a composition that has a greater attractant force than (9Z)-9,13-tetradecadien-11-ynal alone, and a sustained-release formulation for pest control using said composition. [Means for solving the problem]

[0007] As a result of intensive research into solving the above problems, the present inventors have found that Stenoma catenifer The present inventors have found that the addition of (9E)-9,13-tetradecadien-11-ynal (2), which is a geometric isomer of (9Z)-9,13-tetradecadien-11-ynal (1), the sex pheromone of the moth, increases the number of attractants, leading to the completion of the present invention.

[0008] According to one embodiment of the present invention, the composition comprises at least (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2). Stenoma catenifer A bioactive composition against is provided. In another aspect of the present invention, a method for the sustained release of the composition and the (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) is provided. Stenoma catenifer Control sustained release formulations are provided. In another aspect of the present invention, the sustained release formulation is placed in a field and the (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) are released into the field. Stenoma catenifer A method for controlling the pests is provided. Effect of the Invention

[0009] According to the present invention, more Stenoma cateniferIt is possible to obtain a composition that is effective in specifically attracting male adults of this species and in understanding the occurrence status in more detail. In addition, by using the composition to prepare a sustained release formulation, it is possible to directly control this species by applying it to mass trapping and mating disruption, etc. [Brief description of the drawings]

[0010]

Figure 1

[0011] First, the composition contains at least (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2), Stenoma catenifer This invention describes compositions that are biologically active against Stenoma catenifer As a result of pheromone gland extraction and analysis by GC-EAD (GG-electroantennogram detection: gas chromatography with antenna potential detector), it was reported that three compounds, (9Z)-9,13-tetradecadien-11-ynal (1), (9Z)-9,13-tetradecadien-11-yn-1-ol, and (6Z,9Z)-6,9-tricosadiene, were pheromone candidate compounds (Non-Patent Document 2). Furthermore, in a field attraction test using these three compounds, (9Z)-9,13-tetradecadien-11-ynal (1) was found to be a pheromone candidate compound. Stenoma catenifer The addition of (9Z)-9,13-tetradecadien-11-yn-1-ol reduced the number of attractants, indicating that it was an inhibitor, while the addition of (6Z,9Z)-6,9-tricosadiene had no effect on the number of attractants, indicating that it was an inactive component. Only (9Z)-9,13-tetradecadien-11-ynal (1) Stenoma catenifer It has been identified as the sex pheromone of the insect (Non-patent Documents 2, 3).

[0012] On the other hand, (9E)-9,13-tetradecadien-11-ynal (2) contained in the composition of the present invention is a geometric isomer of (9Z)-9,13-tetradecadien-11-ynal (1), Stenoma catenifer In addition, it is not a natural pheromone substance. Stenoma catenifer There have also been no reports of extraction from the above data (Non-Patent Document 2).

[0013] In addition, whether compounds that are structurally similar to pheromone substances have the same effect as the pheromone substances varies from insect to insect, and it has been reported that in some cases compounds that are structurally similar to pheromone substances act as inhibitors. For example, Stenoma catenifer In the case of the sex pheromone (9Z)-9,13-tetradecadien-11-ynal (1), the related compound (9Z)-9,13-tetradecadien-11-yn-1-ol, which has the same basic structure as the sex pheromone but has different functional groups, is an attraction inhibitor. Neoleucinodes elegantalis In the case of the sex pheromone of the insect Spodoptera fasciata, (11E)-11-hexadecenol is the main sex pheromone component and (3Z,6Z,9Z)-3,6,9-tricosatriene is the minor sex pheromone component, and it has been reported that the addition of (11Z)-11-hexadecenol, a geometric isomer of the main sex pheromone component (11E)-11-hexadecenol, significantly reduces the number of attractants (Non-Patent Document 4). As such, the effects of sex pheromone analogues and geometric isomers on attraction of a given insect differ from insect to insect, and therefore must be confirmed by actual attraction tests.

[0014] From an economical viewpoint, it is preferable that (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) are artificially synthesized compounds. (9Z)-9,13-tetradecadien-11-ynal (1) can be produced, for example, by a method including at least a step of obtaining a (5Z)-14,14-dialkoxy-1,5-tetradecadien-3-yne compound by a Wittig reaction of 4-penten-2-ynal with a triarylphosphonium dialkoxyalkylide compound, and a step of hydrolyzing the obtained (5Z)-14,14-dialkoxy-1,5-tetradecadien-3-yne compound. On the other hand, (9E)-9,13-tetradecadien-11-ynal (2) can be produced, for example, by a method including at least a step of obtaining a (5E)-14,14-dialkoxy-1,5-tetradecadien-3-yne compound by a Wittig reaction (Schlosser modification) between 4-penten-2-ynal and a triarylphosphonium dialkoxyalkylide compound, and a step of hydrolyzing the obtained (5E)-14,14-dialkoxy-1,5-tetradecadien-3-yne compound.

[0015] The mixing ratio (1):(2) of (9Z)-9,13-tetradecadiene-11-ynal (1) and (9E)-9,13-tetradecadiene-11-ynal (2) is not particularly limited as long as it is within the range in which male adult insects are attracted, but is preferably 100:0.5 to 100:600, more preferably 100:1 to 100:400, even more preferably 100:10 to 100:350, and particularly preferably 100:33 to 100:300, in mass ratio. (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) may contain impurities that are unavoidable during production.

[0016] The bioactive composition may contain, as an additive, antioxidants such as 2,6-ditert-butyl-4-methylphenol (BHT), butylhydroxytoluene, butylhydroxyanisole, hydroquinone, vitamin E, etc.; ultraviolet absorbers such as 2-hydroxy-4-octyloxybenzophenone, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (HBMCBT), etc. When the bioactive composition is used in a sustained release formulation, the additive may be a compound that is released together with (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2), or a compound that is not released and remains. The content of each additive in the physiologically active composition is, for example, 0.5 to 50 mass% for the antioxidant and 0.5 to 50 mass% for the ultraviolet absorber, relative to the total amount of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2).

[0017] Next, a sustained release formulation comprising a physiologically active composition and a carrier or container for sustained release of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in the physiologically active composition is described. The release of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) into a field is not particularly limited as long as it can control the pests. For example, a sustained release formulation having a carrier impregnated with the physiologically active composition or a sustained release formulation having a container such as a cap, tube, capsule, ampoule, can or bag containing the physiologically active composition is used.

[0018] The sustained-release formulation may be any formulation that can sustainably release an active ingredient such as a pheromone compound from a carrier or container, etc., in small amounts for a desired period of time for pest control or other purposes, and examples of such formulations include lure formulations, reservoir-type formulations, matrix formulations, aerosol formulations, and spray-type formulations. In this case, it is sufficient that the active ingredient such as a pheromone compound can be released, for example, into a farm field, regardless of whether it is released actively or passively from a carrier or container, etc.

[0019] Stenoma catenifer The controlled release formulation for pest control comprises a physiologically active composition and a carrier or container for controlled release of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in the physiologically active composition. The sustained release preparation comprising a carrier can be manufactured by known techniques, such as kneading or impregnation into the carrier. The shape and size of the carrier vary depending on the application method and application amount. For example, in the case of a hand-applied preparation comprising a ring-shaped carrier, the ring diameter is preferably 0.01 to 5 m, and in the case of a spray preparation comprising a granular carrier having a spherical or elliptical shape, the diameter of the particle (long side in the case of an ellipse) is preferably 0.01 to 10 cm. The amount of the carrier to be supported varies depending on the application method and application amount, but is preferably 0.01 mg to 100 g, more preferably 1 mg to 10 g per preparation.

[0020] The sustained-release preparation equipped with a container can be produced by known techniques, for example, a method of injecting the physiologically active composition or the like into a polymeric tubular container and sealing both ends of the tube, or a method of filling the physiologically active composition or the like into a can and attaching a valve capable of spraying.

[0021] The sustained-release preparation provided in the container may contain a diluent as necessary. Examples of diluents include hydrocarbons such as hexane, heptane, octane, nonane, decane, and toluene; esters such as ethyl acetate and n-butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and dibutyl ether; nitriles such as acetonitrile and propionitrile; aprotic polar solvents such as N,N-dimethylformamide; mineral oils such as kerosene, liquid paraffin, amber oil, and creosote oil; vegetable oils such as castor oil, linseed oil, salad oil, corn oil, soybean oil, sesame oil, rapeseed oil, safflower oil, sunflower oil, palm oil, olive oil, peanut oil, almond oil, grapeseed oil, jojoba oil, rosehip oil, avocado oil, hazelnut oil, and orange oil; animal oils such as fish oil, lanolin oil, squalane, egg yolk oil, cod liver oil, horse oil, and mink oil; and synthetic oils such as ester oil. The amount of the diluent added is preferably 0 to 10,000 parts by mass relative to 100 parts by mass in total of the (9Z)-9,13-tetradecadien-11-ynal (1) and the (9E)-9,13-tetradecadien-11-ynal (2).

[0022] A propellant is used for sustained release preparations that have a can as a container. The propellant may be one or more of the following: liquefied petroleum gases such as propane, propylene, n-butane, isobutane, and dimethyl ether (hereinafter also referred to as "DME"); halogenated carbon gases such as HFC-152a, HFC-134a, HFO-1234yf, and HFO-1234ze; carbon dioxide; nitrogen gas; and compressed gases such as compressed air. In terms of the control effect, the mass ratio of the total amount of (9Z)-9,13-tetradecadien-11-ynal (1), (9E)-9,13-tetradecadien-11-ynal (2), the additives and the diluent to the propellant is preferably 80:20 to 25:75, and more preferably 45:55 to 65:35. The filling amount of a sustained release formulation having a can as a container is preferably 0.01 mg to 500 g, more preferably 1 mg to 200 g, from the viewpoint of control effect.

[0023] The sustained release preparation equipped with a tubular container is suitable because it has a long period of time for releasing (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) and the like, and the release is uniform. In order to maintain the release at a moderate rate, the inner diameter is preferably 0.01 to 5.0 mm, and the wall thickness is preferably 0.05 to 3.0 mm.

[0024] In the case of reducing the number of release sites without changing the dosage per unit area, it is desirable to change the length of the sustained release preparation having a tubular container without changing the loading amount per unit length of one sustained release preparation having a tubular container. The length is preferably 0.2 to 100 m, more preferably 0.5 to 20 m, and even more preferably 1 to 10 m. However, this is not the case when the sustained release preparation having a tubular container is connected in two or more series. In this case, the loading amount per 1 m of one sustained release preparation having a tubular container is preferably 0.005 to 5.5 g.

[0025] The carrier of the sustained-release preparation is not particularly limited as long as it can stably hold the physiologically active composition and release at least (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in the physiologically active composition for a certain period of time. Examples of such materials include natural rubber such as cis-polyisoprene, synthetic rubber such as isoprene rubber and butadiene rubber, polyolefin such as polyethylene and polypropylene, sodium metasilicate, silica gel, quartz, polylactic acid, polycaprolactone, polyhydroxyalkanoate, polyglycolic acid, polybutylene succinate, modified polyvinyl alcohol, casein, modified starch, polyhydroxyalkanoic acid such as polyhydroxybutyric acid, polysaccharide derivatives such as cellulose and acetylcellulose, minerals such as zeolite, etc.

[0026] The container of the sustained-release preparation is not particularly limited as long as it is made of a material that can release at least the ((9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in the physiologically active composition for a certain period of time, and examples of the container include those made of a polymer or metal. As the polymer, a material through which (9Z)-9,13-tetradecadiene-11-ynal (1) and (9E)-9,13-tetradecadiene-11-ynal (2) and the like can permeate and be released to the outside of the polymer membrane at a moderate speed is preferred, and examples thereof include natural rubber exemplified by cis-polyisoprene, synthetic rubber exemplified by isoprene rubber, butadiene rubber, and acrylonitrile-butadiene rubber (NBR), polyolefin exemplified by polyethylene and polypropylene, copolymers containing 80% by weight or more of ethylene exemplified by ethylene-vinyl acetate copolymer and ethylene-acrylic acid ester copolymer, biodegradable plastics exemplified by polylactic acid, polycaprolactone, polyhydroxyalkanoate, and cellulose, polyethylene, polypropylene, vinyl acetate and vinyl chloride, polytetrafluoroethylene, etc., and from the viewpoints of economy and versatility, synthetic rubber, ethylene-vinyl acetate copolymer, and polylactic acid are preferred. These polymers can also be used as spray containers by suppressing permeation by increasing the membrane thickness. The metal may be any metal that can be used for spraying or scattering, such as aluminum, stainless steel, or steel.

[0027] Next, the method includes at least a step of placing a sustained release formulation comprising a physiologically active composition containing at least (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) and a carrier or container for sustained release of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in the physiologically active composition in a field, and releasing (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in the sustained release formulation into the field.Stenoma catenifer This article explains how to control this pest. Stenoma catenifer Examples of the control method include mass trapping or attract and kill, push-pull, attract and infect, and mating disruption. According to the present invention, the sustained release formulation is particularly effective in preventing the growth of pests in fields. Stenoma catenifer The present invention can be preferably applied to these control methods that target the above-mentioned pests. Stenoma catenifer The release of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in the physiologically active composition into a field is not particularly limited as long as it can control the pests, but it is preferable to use, for example, the above-mentioned sustained release formulation actively or passively. Active methods include spraying or scattering from a can, a spray bottle, a sprinkler, or an irrigation system. Passive methods include permeation or release (sustained release) from a container or a carrier.

[0028] The application of the sustained release formulation to the field is not particularly limited, but for example, the application density of the sustained release formulation is uniformly 0.10 to 2000 places / ha, preferably 0.25 to 1000 places / ha within the field where control is performed. The amount of release from one release point varies depending on the field environment, weather conditions, etc., but is not particularly limited as long as it is an amount that can be uniformly dispersed in the field, and is preferably 0.001 to 20 g / day / ha. In this way, the avocado pests in North, Central and South America, Stenoma catenifer can be prevented. The claims of the original application of this application, Patent Application No. 2021-106294, as originally filed are as follows: [Claim 1] At least (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2), Stenoma catenifer A composition that is biologically active against [Claim 2] The composition according to claim 1, wherein the mass ratio of the (9Z)-9,13-tetradecadiene-11-ynal (1) to the (9E)-9,13-tetradecadiene-11-ynal (2) is 100:0.5 to 100:600. Stenoma catenifer A composition that is biologically active against [Claim 3] A method for the preparation of a pharmaceutical composition comprising the physiologically active composition according to claim 1 or 2, and a carrier or container for sustained release of the (9Z)-9,13-tetradecadien-11-ynal (1) and the (9E)-9,13-tetradecadien-11-ynal (2). Stenoma catenifer Sustained release formulation for pest control. [Claim 4] The method includes at least a step of placing the sustained release formulation according to claim 3 in a field and releasing the (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) into the field. Stenoma catenifer How to prevent this. EXAMPLES

[0029] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. Example 1 To 1.2 mg of a mixture of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in a mass ratio of 100:300, BHT (2,6-di-tert-butyl-4-methylphenol) and HBMCBT (2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole) were added as stabilizers so as to contain 2% by mass each, Stenoma cateniferA composition having physiological activity against the schizophrenia was prepared. The composition was supported on a rubber cap made of isoprene to prepare a sustained release formulation. A white sticky trap was used to evaluate the sustained release formulation. As shown in Figure 1, the white sticky trap consists of a roof and a bottom plate, and the entrance for insects is designed to be narrow. A sticky substance is attached to the top surface of the bottom plate, and sustained release formulation A is placed directly on the sticky surface. In other words, the trap is designed to capture only insects that approach the sustained release formulation, and to prevent non-target insects from flying in as much as possible. Between September 23 and November 25, 2019, traps containing each sustained-release preparation were Stenoma catenifer The traps were placed in orchards where the males live. The number of male adults killed by each trap was counted every 7 days. The total number of the traps killed by the sustained release formulation of Example 2 described below was set to 100, and the relative value of the number of the traps killed by the sustained release formulation of Example 1 was calculated to evaluate the control effect. The results are shown in Table 1.

[0030] Example 2 Except for changing the amount of the mixture to 0.6 mg of a mixture of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in a mass ratio of 100:100, the preparation and evaluation of the control effect were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0031] Example 3 Except for changing the amount of the mixture to 0.4 mg of a mixture of (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2) in a mass ratio of 100:33, the preparation and evaluation of the control effect were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0032] Comparative Example 1 Except for changing the 1.2 mg of the mixed solution in Example 1 to 0.3 mg of (9Z)-9,13-tetradecadien-11-ynal (1), the production and evaluation of the control effect were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0033] [Table 1]

[0034] In all the tests of Examples 1 to 3 and Comparative Example 1, the amount of (9Z)-9,13-tetradecadien-11-ynal (1) supported was the same, 0.3 mg. The attractants of Examples 1 to 3 had more larvae than the attractant of Comparative Example 4. Stenoma catenifer The attraction and killing of adult males was observed. Thus, it was confirmed that the addition of (9E)-9,13-tetradecadien-11-ynal (2) increased the total number of insects attracted. [Explanation of symbols]

[0035] A. Sustained release preparations

Claims

[Claim 1] A composition which is biologically active against Stenoma catenifer, comprising at least (9Z)-9,13-tetradecadien-11-ynal (1) and (9E)-9,13-tetradecadien-11-ynal (2).

Images