KR20200052626A - A composition for a repellent against Grapholita molesta, and producing methods of its carriers - Google Patents

Abstract

The present invention relates to a composition for repelling male Grapholita molesta, a carrier thereof and a method of preparing the same. More specifically, compounds E8-12OH, Z8-12Ald and E8-12:Ald, which are isomers, are prepared from Z8-12Ac, E8-12Ac and Z8-12OH known as a sex pheromone component of female Grapholita molesta, and an electrophysiological response to a sensory organ of male Grapholita molesta and an effect of canceling attractive force of sex pheromones outdoors are examined by using the isomers, wherein the sensory organ responses strongly when Z8-12Ald is mixed with sex pheromones, and the attractive force of sex pheromones is greatly reduced even in an outdoor examination when the substance is mixed with the sex pheromones, thereby having an effect of repelling male Grapholita molesta. Therefore, the composition of the present invention may be very useful for pest control of Grapholita molesta and the like.

Description

A composition for a repellent against Grapholita molesta, and producing methods of its carriers

The present invention relates to a composition for repelling male peach moths, a carrier thereof and a method for manufacturing the same.

In general, peach net moth ( Grapholita molesta ) is a pest that occurs in nuclear fruit such as apples, peaches, pears, plums, plums, or apricots. The hatched larvae eat and enter the tip of Shincho, and the damaged Shincho dies because the tip is bent and dies, releasing gin and shit. In addition, the larvae penetrate through the fruit, and mainly penetrate into the calyx, causing damage.

Since it usually occurs over 4 ~ 5 generations in a year, the number is huge, and the first generation mainly applies new shoots, and after the second generation, fruit is mainly applied. If the larva penetrates the fruit, it is controlled even if pesticides are sprayed. It is important to spray the agent before the hatched larvae enter the fruit because of the poor effect. To determine this period, farms have used sex pheromone traps.

The female sex pheromone component of peach net moth is (Z) -8-dodecenyl acetate (Z8 dodecenyl acetate, hereinafter Z8-12Ac), (E) -8-dodecenyl acetate (E8 dodecenyl acetate, hereinafter E8-12Ac), ( It is known to consist of Z) -8-dodecen-1-ol (Z8 dodecenyl alcohol, hereinafter Z8-12OH). Therefore, conventionally, it has been used as a copulation disturbance or a sex pheromone trap using the sex pheromone component, but these prior arts operate the control of a peach net moth by attracting and collecting male peach net moths. It cannot be fundamentally blocked from entering the circle.

Republic of Korea Patent Publication No. 10-2015-0046436 Republic of Korea Patent Publication No. 10-2016-0056774 Republic of Korea Patent Publication No. 10-2018-0020357

Therefore, the present invention derived in order to solve the above problems, synthesizes an isomerized compound from three components of sex pheromones of female peach net moth (E) -8-dodecen-1-ol (E8 dodecenol, hereinafter) E8-12OH), (Z) -8-dodecenal Z8 dodecenal, hereinafter Z8-12: Ald) and (E) -8-dodecenal (E8 dodecenal, hereinafter E8-12: Ald), of these isomers The electrophysiological response to the sensory period of the peach net moth and the offset effect on the attractive force of sex pheromones in the outdoors, that is, the repelling effect on the males, were examined. As a result, in the electrophysiological experiment of the peach net moth antenna, when the Z8-12Ald was mixed with sex pheromone, the sensory organs reacted strongly, and even in outdoor demonstration experiments, when this material was mixed with sex pheromone, the attractive force of sex pheromone was greatly reduced and peach net The present invention was completed by confirming that the male of the moth avoids this material.

Accordingly, an object of the present invention is to significantly reduce the attraction effect of female pheromones of peach pure moths to prevent male peach pure moths from entering the orchard.

In order to achieve the above object, in one embodiment of the present invention, at least one of three isomers of peach net moth female sex pheromone, namely Z8-12: Ald, E8-12: OH or E8-12: Ald Provided is a composition for repelling a peach net moth.

Here, the composition may be diluted in sex pheromones selected from at least one of sex pheromones Z8-12: Ac, E8-12: Ac or Z8-12: OH.

In addition, in another embodiment of the present invention provides a composition for repelling male peach net moths in which the composition is incorporated into an agriculturally or horticulturally acceptable carrier.

According to the present invention as described above, by installing one component of the above isomers in an orchard such as a peach, apple or pear, the pests of these crops are prevented from flying into the orchard, which is the root of the peach net moth male. It has the effect of blocking the inflow to the, and thus preventing the female in the orchard from mating with the male. If a female does not mate with a male, it will produce an asterisk, and the aegran does not hatch, so it is possible to achieve an environmentally friendly control purpose.

In addition, the composition according to the present invention has a relatively low synthesis cost, and can be used for controlling pests such as peach net moth by preparing a simple carrier and hanging it on a tree.

The effects according to the present invention in the above are not limited to the above, and other effects of the present invention are clearly understood by those skilled in the art to which the present invention pertains through the examples and claims described below. Will be understandable.

1 shows the synthesis of Z8-12Ald of the present invention.
Figure 2 shows the synthesis of E8-12OH and E8-12Ald of the present invention.
Figure 3 shows the mass-spectrum of the Z8-12Ald of the present invention.
Figure 4 shows the Mass-spectrum of E8-12OH of the present invention.
Figure 5 shows the mass-spectrum of the E8-12Ald of the present invention.
Figure 6 shows the electrical response of the male sensory group to E8-12: OH, Z8-12: Ald, E8-12: Ald of the present invention.
FIG. 7 shows the inducing effect of E8-12: Ald and Z8-12: Ald of the present invention on the spring generation peach net moth male.
Figure 8 shows the incentive effect on the autumn generation peach net moth male of E8-12: Ald and Z8-12: Ald of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a composition for repelling male peach moths, a carrier thereof and a method for manufacturing the same.

Specifically, isomeric compounds were synthesized from Z8-12Ac, E8-12Ac, and Z8-12OH, known as sex pheromone components of female peach net moths, and these isomers were E8-12OH, Z8-12: Ald and E8-12: It was named Ald.

In addition, using the isomers of the present invention, the electrophysiological reaction to the sensory period of male peach net moths and the effect of counteracting the attractive force on males of sex pheromones in the field were examined. As a result, when Z8-12: Ald was mixed with sex pheromone, the male sensory effect of the peach net moth strongly reacted, and even in outdoor black, when this material was mixed with sex pheromone, the attractive force of sex pheromone to males was significantly reduced. In Z8-12; Ald was confirmed to have a strong repellent effect on the male of this pest.

Specifically, in one embodiment of the present invention, a composition for controlling a peach net moth comprising at least one of Z8-12: Ald, E8-12: OH or E8-12: Ald is provided.

Here, the isomers Z8-12: Ald, E8-12: OH, and E8-12: Ald can be diluted in Z8-12Ac, E8-12Ac, and Z8-12OH, which are sex pheromones of peach net moth females. In addition, Z8-12: Ald, E8-12: OH and E8-12: Ald may be diluted in sex pheromone by mixing at least two or more, but is not limited thereto.

Here, the sex pheromone may be a mixture of Z8-12: Ac, E8-12: Ac, and Z8-12: OH in a volume ratio of 95: 10: 8 to 95: 2: 1, and preferably 95 : 5: 1.

On the other hand, in another embodiment of the present invention provides a method for preparing an isomer having repellent activity against a male peach net moth.

Specifically, a method for preparing an isomer having repellent activity in male peach net moths is sex pheromone selected from Z8-12Ac, E8-12Ac, and Z8-12OH, 2,2,6,6-tetramethylpiperidine-1- Dissolving oxy (2,2,6,6-tetramethylpiperidin-1-oxy) and iodobenzene diacetate in a solvent to react; And diluting ether in the reactant, and washing and drying the organic layer.

Here, the solvent may be acetonitrile (acetonitrile) or a mixed solvent in which CH ₂ Cl ₂ and CH ₃ OH are mixed in a volume ratio of 9: 1.

Further, the pH may be 5.0 to 9.0, preferably pH 7.0.

The temperature may be -10 to 10 ° C, preferably 0 ° C.

The reaction time may be 1 hour to 3 hours, preferably 2 hours.

On the other hand, the organic layer may be washed with one or more of saturated Na ₂ S ₂ O ₃ aqueous solution, 2N aqueous hydrochloric acid solution or saturated brine.

Preferably, the present invention provides a composition for repelling a male peach moth and a carrier thereof.

In the present invention, the carrier may contain an agriculturally or horticulturally acceptable carrier, and may be any suitable solid medium that may contain the repellent composition of the present invention, and the repellent composition of the present invention is suitably externally It can be a porous or breathable medium that enables furnace release.

The novel compound of the present invention can be prepared in a container for release. As a release container (carrier), a conventional pheromone release container including a rubber diaphragm, polyethylene tube, polyphenol tube, porous fiber, various types of plastic fibers, plastic laminate flakes, microcapsules, and the like can be used. Other solid carriers include talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, and calcium carbonate.

Examples of isomer compounds incorporated into the carrier in the present invention may be prescribed in any formulations such as emulsions, liquids, suspensions, hydrating agents, flowables, powders, granules, tablets, emulsions, aerosols, and smokers. Accordingly, examples of the carrier include solid carriers, liquid carriers, gaseous carriers, surfactants, and auxiliary agents such as dispersants.

The amount of the composition of the present invention may vary depending on the type of the container for release, but may preferably be 0.1 to 200 mg, more preferably 1 to 100 mg in the container.

The isomer composition of the present invention is used by being diluted with an organic solvent or an organic solvent, and the dilution ratio can be appropriately selected depending on the carrier for release, but may be preferably diluted 100 to 1200 times. For example, in the embodiment, it may be made of a wax in a liquid state melted in a wax, and the wax may be one or more selected from paraffin wax, beeswax wax, wood wax, or carnauba wax. no.

Examples of the solvent for diluting the isomer for male repelling of peach net moth of the present invention include solvents such as methanol, acetone, and hexane, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, water, and the like.

The carrier, surfactant, dispersing agent and adjuvant may be used alone or in combination, respectively, as necessary.

The content of the active ingredient in the formulation is not particularly limited, and is usually 1-75% by weight in an emulsion, 0.3-25% by weight in a powder, 1-90% by weight in a hydrating agent, and 0.5-10% by weight in a granule.

The novel compound according to the present invention has a relatively low synthesis cost, and can be used for controlling pests of peach net moths by preparing a simple carrier and hanging it on a tree.

In the case of the repellent composition in the present invention, a liquid agent is put in various containers to be applied to a method of volatilizing the repellent material into the atmosphere by installing the fruit tree in a certain distance at a certain distance to avoid peach sprout moth, preferably peach sprout moth. Can be.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the following examples are only intended to materialize the contents of the present invention, and the present invention will not be limited thereby.

<Example 1> Materials and methods

Synthesis method of 1-1 isomer (synthesis of Z8-12: Ald, E8-12: OH, E8-12: Ald)

The synthesis method of Z-8-dodecenal (hereinafter, Z8-12: Ald) is as follows. Z8-12: OH (Z-8-dodecen-1-ol, Bedoukian research, Danbury, CT, USA)) 1.5 g, 8.15 mmol, pH 7.0 buffer solution (Bedoukian research, Danbury, CT, USA) 8 mL, 2 , 2,6,6-tetramethylpiperidin-1-oxy (2,2,6,6-tetramethylpiperidin-1-oxy, TEMPO, Alfa Aesar) 130 mg, 0.87 mmol and iodobenzene diacetate ) 2.9 g, 8.97 mmol was dissolved in 8 mL of acetonitrile at 0 ° C. The reaction solution was reacted at 0 ° C for 2 hours, and then diluted with ether. The organic layer was washed twice with a saturated Na ₂ S ₂ O ₃ aqueous solution and once with saturated brine and then dried. After concentration, Z8-12: Ald of 97.7% purity was obtained using a silica gel chromatogram (FIG. 1).

E-8-dodecen-1-ol (E8-12: OH) was obtained by alkali hydrolysis of the corresponding acetate. E8-12: Ac (E-8-dodecenyl acetate, Bedoukian Research) 4.0 g, 17.7 mmol was dissolved in a mixed solvent in which CH ₂ Cl ₂ and CH ₃ OH were mixed in a volume ratio of 9: 1, and the final alkali concentration was 0.2N. When possible, 17.7 mL of a 2N NaOH methanol solution was added and reacted for 2 hours. After removing the solvent, the mixture was diluted with water, and the aqueous layer was extracted with ether, washed with a 2N aqueous hydrochloric acid solution and saturated brine, and dried. After concentration, E8-12: OH with a purity of 99.0% or more was obtained using a silica gel chromatogram (A in FIG. 2).

E-8-dodecenal (hereinafter, E8-12: Ald) was synthesized using E8-12: OH (E-8-dodecen-1-ol) synthesized above, and the synthesis method was Z8-12: Ald. It was synthesized in the same manner as in the production method, to obtain a substance of 95.6% purity (Fig. 2B).

Z8-12: Ald, E8-12: OH, E8-12: Ald synthesized above were measured by GC-Mass (gas chromatograph-mass spectrometer), and mass-spectrum is shown in FIGS. 3, 4 and 5 It was confirmed as follows.

<Example 2> Electrophysiological response of male sensation period (antenna) of peach net moth to sex pheromone isomer

2-1 Experiment method

Peach net moth female sex pheromone components Z8-12: Ac, E8-12: Ac, Z8-12: OH, and isomers of the sex pheromone components prepared in Example 1, Z8-12: Ald, E8-12: Ald, E8-12: OH was used to test the electrophysiological reaction of the male antenna of the peach net moth. Each material was diluted with a concentration of 100 μg / ml in hexane solution and used.

After the fable, the antennae of male adult peach net moths, which are 1 to 3 days old, were cut and attached with a cut antenna base to the reference electrode part using electro gel, and the antenna end was slightly cut and contacted with the recording electrode part. After dispensing 10 ul of other substances into filter paper, put them in pasteur pipette, and then stimulate each component to the antenna to confirm the antenna response. Each component was randomly selected and used in the experiment.

2-2 Results

The electrical response of male antennae to female pheromones and isomers of peach net moths is shown in FIG. 6. According to FIG. 6, when E8-12: OH, E8-12: Ald and Z8-12: Ald, respectively, were mixed with sex pheromones, the reaction was significantly greater than that of untreated and hexane. In these results, it means that male peach moths respond to sex pheromones and these substances.

<Example 3> Repelling effect of male sex pheromones and each isomer Field verification experiment

3-1 Experimental method

An outdoor experiment was conducted using Z8-12: Ald, E8-12: Ald, which are antennae reactions among female pheromones of the peach net moth and its isomers. St. pheromone lure of peach net moth was prepared by mixing three components of Z8-12: Ac, E8-12: Ac, and Z8-12: OH in a volume ratio of 95: 5: 1 respectively.

In addition, pheromone lures using isomers were prepared by adding Z8-12: Ald and E8-12: Ald to the peach net moth female sex pheromone lures by 1 mg and 10 mg, respectively.

The outdoor experiment was conducted at the apple orchard in Hamyang, Gyeongnam, and the trap was installed at a height of 1-1.5m on an apple tree or other subsidiary facilities with a distance of 12m between each iteration and a trap between each trap of about 14m. Traps were examined at weekly intervals to determine the number of male peach net moths.

3-2 Results

Of the three isomers of peach net moth, sex pheromones, Z8-12: Ald and E8-12: Ald are mixed with 1 mg and 10 mg of St. Pheromone Luer and installed outdoors, after which the sex pheromone attraction effect (ie, Evasion effect). 7 is an experimental result for the spring generation, and FIG. 8 is an experimental result for the autumn generation.

St. pheromone is a substance that strongly attracts males of peach net moths. In the spring generation, Z8-12: Ald is 1mg or 10mg when mixed with st. Pheromone, which has the lowest attraction. The same was true for the autumn generation. These results indicate that Z8-12: Ald greatly offsets the attractiveness of peach net moth sex pheromones.

Conversely, E8-12: Ald had the highest attraction when mixed with sex pheromones. In particular, E8-12: Ald was found to increase the attractive force of sex pheromones when mixed with sex pheromones.

As described above, the present invention was synthesized by newly synthesized isomers of the female pheromone moth female pheromone component Z8-12; Ald to investigate the reaction of male peach moth moths, and a strong repelling effect against this pest was confirmed. Z8-12; Ald according to the present invention can maximize the effect of peach net moth control by using it with a peach net moth sex pheromone trap. For example, while collecting a peach net moth with a peach net moth sex pheromone trap, the control composition containing Z8-12; Ald of the present invention is hung on a tree to prevent the peach net moth from approaching the female to mate. Can be. In addition, by installing Z8-12; Ald according to the present invention in a peach, apple, or pear orchard, peach net moth, which is a target pest of these crops, can be prevented from flying to the orchard and can be used for pest control.

As described above, specific embodiments of the present invention have been described in detail, but those skilled in the art who understand the spirit of the present invention may add other components within the scope of the same spirit, change, delete, etc., and degenerate other inventions. However, other embodiments included within the scope of the inventive concept may be easily proposed. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of the present invention is indicated by the scope of the claims, which will be described later, rather than the detailed description above, and all the changed or modified forms derived from the meaning and scope of the claims and their equivalent concepts are included in the scope of the present invention. It should be interpreted as.

Claims (3)

Peach containing at least one of Z-8-dodecenal (Z8-12: Ald), E-8-dodecen-1-ol (E8-12: OH) or E-8-dodecenal (E8-12: Ald) A composition for repelling pure moth males.
According to claim 1,
The composition is characterized in that the female peach net moth is diluted with a sex pheromone selected from at least one of Z8-12: Ac, E8-12: Ac or Z8-12: OH component of female peach net moth. Repellent composition.
A composition for repelling peach net moths, characterized in that the composition of any one of claims 1 or 2 is incorporated into an agriculturally or horticulturally acceptable carrier.

Images