KR20030070222A - Chemical compound having acaricidal activity and indicator - Google Patents

Abstract

PURPOSE: An acaricidal compound containing 1,4-benzoquinone, 1,4-dihydroxynaphthalene or the like having an acaricidal effect on Dermatophagoides pteronyssinus or Dermatophagoides farinae is provided. The 1,4-benzoquinone and 1,4-dihydroxynaphthalene can be used as an acarid indicator by causing all acarids to change color to a black color or black-brown color regardless of live or dead insects in all concentrations. CONSTITUTION: The acaricidal compound is one or more selected from the group consisting of 1,4-benzoquinone, 4-hydroxynaphthalene, 8-hydroxyquinaldine, α-naphthoquinoline, α-naphthoquinone, quinaldine, quinazoline, quinoline, quinoline-4-carboxaldehyde, 8-quinolinol and quinoxaline. The compound shows acaricidal activity against Dermatophagoides pteronyssinus or Dermatophagoides farinae. The acarid indicator contains 1,4-benzoquinone, 1,4-dihydroxynaphthalene.

Description

Acaricide Compounds and Pest Indicators {CHEMICAL COMPOUND HAVING ACARICIDAL ACTIVITY AND INDICATOR}

[TECHNICAL FIELD OF THE INVENTION]

The present invention relates to acaricidal compounds and pest indicators, and more particularly to 1,4-benzoquinone and 1,4-dihydroxynaphthalene which discolor the compounds having pesticidal properties and pests into black or dark brown. It is about.

[Private Technology]

The most important species belonging to the pyroglyphid are the dermatophagoides pteronyssinus Hughus and the dermatophagoides farinae Trouessart. Both species show a worldwide distribution of habitats and are the major allergens frequently observed in household dusts (Anonymous, 1989, 83,416-427; Anonymous, 1992, Report of a second International Workshop.Journal of Allergy Clinincal Immunology 89,1046). -10) If these populations thrive, especially in families with asthma or the elderly, the disease can be exacerbated.

In recent years, changes in the residential environment, such as the increase in apartment generation, the increase in the use of auxiliary heating systems, and the increase in the amount of carpets that always exist in the house, have given optimal conditions for the growth of ticks. Rapid multiplication and survival under four seasons (Susan MP and Ward GW Jr, 1987, Immunol.Allergy North Amer 7, 447-461; Pollart SM, Ward GW Jr and Platts-Mills AE, 1989, Immunol Allergy Clinics of North America 7, 447-461)

To reduce the population of house dust mites, physical control such as thorough cleanliness, drying, and relative humidity control in the air, γ-BHC, pirimiphos-methyl, benzyl benzoate, It has been highly dependent on compounds such as diethyl-m-toluamide (DEET) and dibutyl phthalate (Heller-Haupt A. and Busvine JR, 1974, Journal of Medical Entomology 11). , 551-558)

Despite the various control methods for controlling house dust mites mentioned above, due to the difficulty of physical control and low aggression of natural product control agents, researches of various countries have been trying to find powerful and safe compounds with new functionality among known compounds. Active progress is made (Pollart SM, Ward GW Jr and Platts-Mills AE, 1987, Immunol Allergy Clinics of North America 7, 447-461). In this respect, it may be best to identify new functions as house dust mite control agents of known compounds. Because the existing compounds have a variety of bioactive substances, most of these compounds are not only stable in stability but also known to be easily biodegradable, and can selectively kill the specific purpose filling, as well as comprehensive synthesis of house dust mites. This is because it can be used as an integrated mite management program (IPM) source (Namba T., 1993, Hoikusha, Osaka, Japan). Therefore, a lot of research efforts have been made as a commercial dust mite control agent or its lead compound. The focus is on identifying new functions of existing known compounds.

In addition, despite the presence of natural and organic compounds as a powerful house dust mite control agent, invisible house dust mites can cause more serious problems by acting as an allergen in families where asthmatics or the elderly live. The development of indicators that can be identified as is urgent worldwide. Globally, the study of house dust mites is concentrated on the killing ability, so there is no research on the identification indicator. In this respect, not only the development of house dust mite control agents, but also the development of indicators capable of visually identifying house dust mites are required.

Therefore, an object of this invention is to provide the compound which has acaricide.

An object of the present invention is to provide a method for eradicating ticks using acaricide compound.

It is an object of the present invention to provide acaricides containing acaricide compound.

It is an object of the present invention to provide an indicator compound capable of discoloring pests to identify the presence of pests.

It is an object of the present invention to provide compounds which function as acaricide and pest indicators.

1 is an optical microscope photograph of a mite discolored black (or black brown) by 1,4-benzoquinone and 1,4-dihydroxynaphthalene,

Figure 2 is a photograph taken by an optical microscope of the mites killed by a conventional tick acaricide.

In order to achieve the above object, the present invention provides 1,4-benzoquinone (1,4-Benzoquinone), 4-dihydroxynaphthalene (1,4-Dihydroxynaphthalene), 8-hydroxyquinaldine (8-Hydroxyquinaldine), Alpha-naphthoquinoline, alpha-naphthoquinone, quinadine, quinazoline, quinoline, quinoline-4-carboxyaldehyde, quinoline-4- carboxaldehyde), 8-quinolinol, and quinoxaline, one or more selected from the group consisting of acaricide compounds.

The present invention also provides 1,4-benzoquinone, 4-dihydroxynaphthalene, 8-hydroxyquinaldine, alpha-naphthoquinoline, alpha-naphthoquinone, quinaldine, quinazoline, quinoline, quinoline-4-carboxy Provided are acaricides comprising at least one compound selected from the group consisting of aldehydes, 8-quinolinol and quinoxaline.

The present invention also provides a compound for pest display comprising 1,4-benzoquinone or 1,4-dihydroxynaphthalene.

The present invention also provides a pest labeling method comprising inducing a color change of a tick by applying the pest display compound to a tick.

In another aspect, the present invention provides acaricides containing the compound for displaying pests.

Hereinafter, the present invention will be described in detail.

The present inventors screened compounds showing acaricidal activity against ticks among existing compounds, and identified compounds having acaricide.

The acaricidal compound of the present invention is 1,4-benzoquinone (1,4-Benzoquinone) of formula (1), 4-dihydroxynaphthalene (1,4-Dihydroxynaphthalene) of formula (2), 8-hydroxyquinaldine of formula (3) (8-Hydroxyquinaldine), alpha-naphthoquinoline of formula 4, alpha-naphthoquinoline of formula 5, alpha-naphthoquinone of formula 5, quinaldine of formula 6, quinazoline of formula 7 ), Quinoline of formula 8, quinoline-4-carboxaldehyde of formula 9, 8-quinolinol of formula 10, and quinoxaline of formula 11 .

(Formula 1) (Formula 2) (Formula 3)

(Formula 4) (Formula 5) (Formula 6)

(Formula 7) (Formula 8) (Formula 9)

Formula 10

The acaricidal compounds of the present invention cause insecticides of all kinds of mites, and are particularly effective against American house dust mite ( Dermatophagoides farinae ) and vertical house dust mite ( Dermatophagoide pteronyssinus ).

The present invention provides acaricides containing the acaricide compound. Acaricides preferably contain 0.01 to 40% by weight of acaricide compound, alone or in a mixture. However, the content of the biocidal compound is more preferably applied differently according to the formulation of the pesticide, the spraying method.

The acaricide of the present invention is used where a mite is inhabited, and the use method is preferably a coating treatment, dipping treatment, fumigation treatment, or the like, and more preferably, a volatile poison or a contact poison is used to kill the tick. Preferably it is used as a volatile poison or a fumigated poison. The acaricide of the present invention may be used for controlling pests other than mites. The application amount of acaricide may be used in an amount to which conventional insecticides are applied. The formulation of the composition may be a liquid, emulsion, smoker, fumigant, coating agent, granules, solids and the like.

In addition, the acaricide may further include an excipient according to the method of use. The excipient preferably uses an appropriate material according to the use and application method of the composition, more preferably a material included in a conventional pesticide formulation.

Also, 1,4-benzoquinone, 1,4-dihydroxynaphthalene, 8-hydroxyquanaldine, alpha-naphthoquinoline, alpha-naphthoquinone, quanaldine, quenazoline, quinoline, querine of the present invention Norline-4-carboxyaldehyde, 8-quanolinol or quinosarane can be used as substrates for parent compounds for novel compounds that have acaricide activity and have a variety of effects. The parent compound can remove or remove the problematic properties by adding or removing various other chemical structures including hydroxyl, aldehyde, alcohol, amide, and aryl groups through chemical synthesis based on the structure of a known substance. Refers to a new substance that enhances its effectiveness.

In addition, the acaricidal compound of the present invention preferably includes a pest indicator. An indicator referred to in the present invention (Indicator) refers to the action on the pest to identify the pest so that the naked eye can easily identify. Indicators of the invention are 1,4-benzoquinone or 1,4-dihydroxynaphthalene. The two indicators make all kinds of pests discolored black or black brown to identify them (FIG. 2).

The pest indicator of the present invention can identify the population and habitat of the pest, which is effective in removing pests, and can prevent allergens caused by insects in advance. In addition, 1,4-benzoquinone and 1,4-dihydroxynaphthalene have its own acaricide effect and have two functions of killing and marking ticks.

The pest indicator compound of the present invention may be used alone to be used for the purpose of identifying pest populations and habitats, and may be used in addition to compositions such as insecticides. When the indicator compound of the present invention is used as an additive, the content thereof is preferably 0.01 to 40% by weight. However, the content of the indicator compound is more preferably applied differently depending on the formulation of the pesticide, spraying method.

The composition comprising the pest indicator of the present invention is preferably prepared by the same method as the conventional method of use and formulation of the pesticide, but can be prepared by conventional methods and formulations for identifying pests.

Accordingly, it is possible to provide an indicator composition comprising the 1,4-benzoquinone or 1,4-dihydroxynaphthalene parent nucleus compound of the present invention.

The indicator composition of the present invention is preferably discolored black (or black brown) with respect to dead mites or live mites exposed to the composition, and black (or black brown) even with common insecticides or naturally dead mites. The color change effect to) is shown. In addition, the indicator composition of the present invention has an insecticidal or discoloring effect on a common pest. Representative pests include greenhouse dusts, spotted mites and aphids.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.

Example 1: Acaricide Compound

1,4-benzoquinone, 1,4-dihydroxynaphthalene, 8-hydroxyquinaldine, 8-quinolinol, quinoline, quinoline-4-carboxyaldehyde, and quinoxaline are fluka, quinaldine , Alpha-naphthoquinone, alpha-naphthoquinoline was purchased from Wako and quinazoline from Aldrich.

Example 2: Acaricidal Assay

(1) tick

Acaricide activity was carried out for two dust mites. The American house dust mite ( Dermatophagoides farinae ) and the vertical house dust mite (European house dust mite, Dermatophagoide pteronyssinus ) were bred in a room with a relative humidity of 75 ± 5% and a temperature of 25 ± 1 ° C. In a 10.5 × 5 cm container, fry feed and mixed vitamins (Ebio agent) were mixed 1: 1, and saline was poured into the breeding room at the bottom of the container having a volume of 17.5 × 17.5 × 17.5 cm. The mites were bred without exposure to acaricide.

(2) acaricide test

The most important point in the search for bioactive substances is the setting of the initial starting concentration. In the present invention, since the morphological characteristics of the tick have a microscopic structure, 1 mg of the sample per 2 ml microtube was set through several preliminary experiments. The compounds of Example 1 were dissolved in 40 μl of methanol at different concentrations (1.0, 0.5, 0.1, 0.05, 0.025, 0.010, 0.004, 0.0025 mg) and treated in a colorless microtube (2 mL) to the wall and lid of the tube. The material was shaken up and down several times to evenly disperse and buried, and then the solvent was volatilized for 1 hour in a freeze dryer. 25 mites were put in each tube and assayed under the conditions of 25 ± 1 ° C.

The ticks were observed under a microscope to select only those with high activity using a fine brush. Assay results were examined under an optical microscope (20 times) after 24 hours of treatment, the subject was considered to have died without any movement by stimulating the appendage and torso with a fine brush. All assays were repeated 5 or more times and a comparison between the means for the rate of fertilization was made using Scheffe's test (SAS Institute, 1996).

The a potency of the 11 compounds of Example 1 is shown in Table 1 (vertical pattern dust mite) and Table 2 (large dust mite). The same letters (a, b) in Tables 1 and 2 indicate that the mean is not statistically different ( P = 0.05, Sheffe test), and the insecticidal rate is expressed by transforming the square of the arc sine.

compound Salvage rate (mean ± standard deviation,%) Treatment Concentration (mg / tube) 1.00 0.50 0.10 0.05 0.03 0.01 0.004 0.0025 1,4-benzoquinone 100a 100a 100a 100a 100a 84.6 ± 1.6b 13.3 ± 1.1 b 0b 1,4-dihydroxynaphthalene 100a 100a 100a 100a 100a 100a 100a 100a 8-hydroxyquinaldine 100a 100a 100a 68.5 ± 2.6 b 25.6 ± 1.6 b 0b 0b 0b α-naphthoquinoline 100a 100a 100a 100a 100a 100a 76.7 ± 2.2b 36.5 ± 1.8 b α-naphthoquinone 100a 100a 100a 100a 100a 100a 100a 55.1 ± 1.9b Quinaldine 100a 100a 100a 100a 86.3 ± 2.4b 53.3 ± 1.8b 0b 0b Quinazoline 100a 100a 100a 100a 100a 83.1 ± 1.8b 25.7 ± 1.2b 0b Quinoline 100a 100a 100a 100a 100a 100a 49.7 ± 2.1b 11.3 ± 0.5 b Quinoline-4-carboxyaldehyde 100a 100a 100a 100a 100a 100a 76.7 ± 1.7 b 30.5 ± 1.2b 8-quinolinol 100a 100a 100a 74.6 ± 1.9b 50.4 ± 2.2b 14.5 ± 1.2b 0b 0b Quinoxaline 100a 100a 100a 100a 100a 65.8 ± 1.5 b 0b 0b Benzyl benzoate 100a 100a 29.5 ± 1.5b 0b 0b 0b 0b 0b Dibutyl phthalate 100a 100a 54.4 ± 1.8b 27.4 ± 1.9b 0b 0b 0b 0b

When treated with 1 mg, 0.5 mg, 0.1 mg of 11 compounds of Example 1 in the vertical dust mites, all showed a 100% abundance. 1,4-benzoquinone, 1,4-dihydroxynaphthalene, alpha-naphthoquinone, alpha-naphthoquinoline, quinoline, quinoline-4-carboxyaldehyde, quinoxaline, quinaldine and quina when treated with 0.05 mg Joline showed 100% agicide rate and 8-hydroxyquinaldine and 8-quinolinol showed a 60% agitation rate.

In addition, when treated with 0.03 mg of compound, 1,4-benzoquinone, 1,4-dihydroxynaphthalene, alpha-naphthoquinone, alpha-naphthoquinoline, quinaline, quinoline-4-carboxyaldehyde, quinoxaline and Quinazolin showed 100% salvage, quinaldine 86.3%, 8-quinolinol 50.4%, and 8-hydroxyquinaldine 25.5%, while the controls benzyl benzoate and dibutyl phthalate were 0% and 29%, respectively. Low agitation rate was shown.

At the lowest concentration of 0.0025 mg, 1,4-dihydroxynaphthalene, alpha-naphthoquinone, alpha-naphthoquinoline, and quinoline-4-carboxyaldehyde showed salvage rate compared to the benzyl benzoate and dibutyl phthalate control It was confirmed that the ratio of the salvage was excellent.

compound Salvage rate (mean ± standard deviation,%) Treatment Concentration (mg / tube) 1.00 0.50 0.10 0.05 0.03 0.01 0.004 0.0025 1,4-benzoquinone 100a 100a 100a 100a 100a 74.1 ± 1.3b 9.3 ± 0.3b 0b 1,4-dihydroxynaphthalene 100a 100a 100a 100a 100a 100a 100a 100a 8-hydroxyquinaldine 100a 100a 100a 59.1 ± 1.5b 12.3 ± 1.1b 0b 0b 0b α-naphthoquinoline 100a 100a 100a 100a 100a 100a 61.2 ± 1.7 b 25.3 ± 1.4 b α-naphthoquinone 100a 100a 100a 100a 100a 100a 100a 39.2 ± 1.3 b Quinaldine 100a 100a 100a 100a 71.2 ± 1.5b 40.1 ± 1.1 b 0b 0b Quinazoline 100a 100a 100a 100a 100a 71.6 ± 1.3b 12.7 ± 0.7b 0b Quinoline 100a 100a 100a 100a 100a 100a 39.2 ± 1.0 b 0b Quinoline-4-carboxyaldehyde 100a 100a 100a 100a 100a 100a 59.5 ± 1.1b 18.7 ± 0.6 b 8-quinolinol 100a 100a 100a 63.2 ± 1.2b 39.5 ± 1.6b 0b 0b 0b Quinoxaline 100a 100a 100a 100a 100a 53.1 ± 1.6b 0b 0b Benzyl benzoate 100a 100a 32.0 ± 1.9b 0b 0b 0b 0b 0b Dibutyl phthalate 100a 100a 62.2 ± 1.6b 29.9 ± 1.7 b 0b 0b 0b 0b

In the large dust mites, 1 mg, 0.5 mg, 0.1 mg treatment of all 11 compounds showed a 100% agicide ratio, 0.05 mg treatment of 1,4-benzoquinone, 1,4-dihydroxynaphthalene, 100% salvage rate was seen in alpha-naphthoquinone, alpha-naphthoquinoline, quinoline, quinoline-4-carboxyaldehyde, quinoxaline, quinaldine and quinazoline, with 59.1% of 8-hydroxyquinaldine and 8-qui Nolinol showed a 63.2% agitation rate. The control group benzyl benzoate and dibutyl phthalate was not able to observe significant acaricide activity from the 0.050 mg level.

Also, at concentrations of 0.0025 mg, 1,4-dihydroxynaphthalene, alpha-naphthoquinone, alpha-naphthoquinoline, quinoline-4-carboxyaldehyde showed acaricide, which was superior to benzyl benzoate and dibutyl phthalate. It could be confirmed that there is a fertilizing effect.

Example 3: Tick Indicator

1,4-benzoquinone and 1,4-dihydroxynaphthalene were assayed for acaricide activity by the method of Experimental Example 1, and the function was identified as an indicator through the discoloration of the tick with the eyes of the experimenter, not the optical microscope.

By the acaricide activity assay carried out in Example 2, the abundance ratio of 1,4-benzoquinone, 1,4-dihydroxynaphthalene and discoloration of ticks were confirmed. Table 3 shows the results for vertical dust mites, and Table 4 shows the results for large leg dust mites.

compound Salvage rate (mean ± standard deviation,%) Treatment Concentration (mg / tube) 1.00 0.50 0.10 0.05 0.03 0.01 0.004 0.0025 1,4-benzoquinone 100a 100a 100a 100a 100a 84.6 ± 1.6b 13.3 ± 1.1 b 0b Tick color Black color Black color Black color Black color Black color Black color Black color Black color 1,4-dihydroxynaphthalene 100a 100a 100a 100a 100a 100a 100a 100a Tick color Black color Black color Black color Black color Black color Black color Black color Black color Benzyl benzoate 100a 100a 29.5 ± 1.5b 0b 0b 0b 0b 0b Tick color invisible invisible invisible invisible invisible invisible invisible invisible Dibutyl phthalate 100a 100a 54.4 ± 1.8b 27.4 ± 1.9b 0b 0b 0b 0b Tick color invisible invisible invisible invisible invisible invisible invisible invisible

Table 3 shows the results of the agicide test for the vertical pattern dust mite, two compounds were applied at 1.0 mg, 0.5 mg, 0.10 mg, 0.05 mg, 0.03 mg, 0.01 mg, 0.004 mg, 0.0025 mg treatment level and The color change of the tick was shown. 1,4-benzoquinone and 1,4-dihydroxynaphthalene discolored all the mole dust mites to black (or black-brown) regardless of worms and live insects at all concentrations used between 1.0 and 0.0025 mg ( 1). Control groups benzyl benzoate and dibutyl phthalate did not discolor the tick (Figure 2).

compound Salvage rate (mean ± standard deviation,%) Treatment Concentration (mg / tube) 1.00 0.50 0.10 0.05 0.03 0.01 0.004 0.0025 1,4-benzoquinone 100a 100a 100a 100a 100a 74.1 ± 1.3b 9.3 ± 0.3b 0b Tick color Black color Black color Black color Black color Black color Black color Black color Black color 1,4-dihydroxynaphthalene 100a 100a 100a 100a 100a 100a 100a 100a Tick color Black color Black color Black color Black color Black color Black color Black color Black color Benzyl benzoate 100a 100a 32.0 ± 1.9b 0b 0b 0b 0b 0b Tick color invisible invisible invisible invisible invisible invisible invisible invisible Dibutyl phthalate 100a 100a 62.2 ± 1.6b 29.9 ± 1.7 b 0b 0b 0b 0b Tick color invisible invisible invisible invisible invisible invisible invisible invisible

Table 4 shows the results of the agicide test for the large dust mite, the two compounds 1.0 mg, 0.5 mg, 0.10 mg, 0.05 mg, 0.03 mg, 0.01 mg, 0.004 mg, 0.0025 mg at the treatment level and tick Color discoloration of 1,4-benzoquinone and 1,4-dihydroxynaphthalene discolored all the large-legged dust mites to black (or black-brown) regardless of worms and live insects at all concentrations used between 1.0-0.0025 mg ( 1). Discoloration was not observed in the use of two control acaricides (benzyl benzoate and dibutyl phtalate) for the large-legged dust mites.

As mentioned above, the acaricide compound of the present invention has excellent acaricide activity, in particular 1,4-benzoquinone and 1,4-dihydroxynaphthalene are black or black all ticks regardless of necrosis and insects. It can be discolored brown and used as a tick indicator.

Claims (8)

1,4-Benzoquinone, 4-dihydroxynaphthalene, 8-Hydroxyquinaldine, alpha-Naphthoquinoline , Alpha-naphthoquinone, quinaldine, quinazoline, quinoline, quinoline-4-carboxaldehyde, 8-quinolinol -Quinineol) and quinoxaline (Quinoxaline) at least one selected from the group consisting of acaricidal compound. The method according to claim 1, wherein the acaricidal compound has an acaricidal effect against the vertical pattern dust mite ( Dermatophagoides pteronyssinus ) or a large leg dust mite ( Dermatophagoides farinae ). 1,4-Benzoquinone, 4-dihydroxynaphthalene, 8-Hydroxyquinaldine, alpha-Naphthoquinoline , Alpha-naphthoquinone, quinaldine, quinazoline, quinoline, quinoline-4-carboxaldehyde, 8-quinolinol -Quinolinol) and quinoxaline (Quinoxaline) acaricide comprising at least one compound selected from the group consisting of. A pest display compound containing 1, 4- benzoquinone or 1, 4- dihydroxy naphthalene. The compound according to claim 4, wherein the pest is selected from the group consisting of mites, greenhouse dusts, spotted mites and aphids. A pest labeling method comprising inducing a color change of a pest by applying the pest display compound according to claim 4 or 5 to the pest. The pest labeling method according to claim 6, wherein the pest is a worm or a live insect. An acaricide comprising a compound for displaying pests according to claim 4 or 5.