JPH0641094A - Cycloalkenyltriazole derivative and noxious life controlling agent - Google Patents

Abstract

PURPOSE:To provide the new compound derivative consisting of a specific cycloalkenyltriazole derivative, capable of preventively controlling sheath blight and blast of rice without giving adverse effect on crops and effective in exterminating aphids, spider mites, etc. CONSTITUTION:The cycloalkenyltriazole derivative of formula II can be produced by reacting an N-acylimide ester or N-acylimide thiol ester derivative expressed by formula I (X is a halogen, methyl, nitro, cyano or trifluoromethyl; (n) is integer of 1-4; Y is a 5-15C beta-chloro-1-cycloalkenyl; A is S or O; B is a 1-4C alkyl) with a hydrazine derivative expressed by the formula RNHNH2 (R is a 1-4C alkyl) (e.g. monomethylhydrazine) in a solvent (e.g. toluene) at room temperature for 24hr, concentrating the toluene layer and purifying by silica gel column chromatography.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel cycloalkenyltriazole derivative and a pest control agent containing the same as an active ingredient.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication No. 56-154464 discloses
It is described that the triazole derivative has insecticidal and acaricidal activity. However, it cannot be said that the compounds specifically described in this publication have sufficient insecticidal and acaricidal activity.

[0003]

The object of the present invention is to provide a novel and useful cycloalkenyltriazole derivative having a further improved pesticidal and control activity including insecticidal and acaricidal activity, without adversely affecting crops, and To provide a pest control agent.

[0004]

The compounds specifically described in Japanese Patent Laid-Open No. 56-154464, which is a conventional technique, can only control a herd of mites, insects or aphids and their eggs or larvae. Have been described.
The present inventors have synthesized various triazole derivatives in order to develop new and useful pest control agents, and have conducted repeated studies on their physiological activities.

As a result, a cycloalkenyltriazole derivative having a β-chloro-1-cycloalkenyl group having 5 to 15 carbon atoms in the substituent at the 5-position of the triazole ring was found to be a rice blight and a blast disease which are serious diseases of rice. Against harmful insects, harmful mites, for example, aphids such as cotton aphids, and extremely excellent killing of mites such as spider mites, kanzawa mites, citrus mites and the like. The present invention was completed by finding out that it has a deteriorating activity.

That is, the present invention is the following cycloalkenyltriazole derivatives and pest control agents. (1) General formula [1]

[Chemical 2] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, a methyl group, a nitro group, a cyano group or a trifluoromethyl group, and n represents an integer of 1 to 4. Y
Represents a β-chloro-1-cycloalkenyl group having 5 to 15 carbon atoms. Here, the cycloalkenyl group of Y has 1 to 1 carbon atoms.
It may be substituted with an alkyl group of 4. ) A cycloalkenyltriazole derivative represented by: (2) A pest control agent comprising the cycloalkenyltriazole derivative according to (1) above as an active ingredient.

The number of carbon atoms represented by R in the general formula [1] is 1
As the alkyl group of 4 to 4, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s
Examples thereof include ec-butyl group and tert-butyl group.

Examples of the halogen atom represented by X in the above general formula [1] include fluorine, chlorine, bromine, iodine and the like. n is an integer of 1 to 4, and when n is 2 or more, the halogen atoms may be the same kind or different combinations.

The number of carbon atoms represented by Y in the above general formula [1] is 5
Examples of the β-chloro-1-cycloalkenyl group of ~ 15 include those shown in Tables 1 to 3 below. This β-chloro-1-cycloalkenyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group to be substituted include those exemplified above for R.

Among the cycloalkenyltriazole derivatives represented by the above general formula [1], compounds having particularly excellent pesticidal and controlling activity are those in which R is a methyl group and Xn is a halogen atom (fluorine, chlorine, bromine or iodine). , These may be the same or different combinations, n is 1
An integer of ~ 4. ), Y is β-chloro-1 having 5 to 15 carbon atoms
A cycloalkenyl group (the cycloalkenyl group may be substituted with a methyl group).

Typical compounds of the cycloalkenyltriazole derivatives represented by the above general formula [1] and their physical properties are shown in Tables 1 to 3. In addition, the compound numbers in the tables are referred to in the subsequent description of the present specification.

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

The cycloalkenyltriazole derivative of the present invention can be produced by the following production method <A>, but is not limited to this method. Manufacturing method <A>

[Chemical 3] (In the formula, A represents a sulfur atom or an oxygen atom, B represents an alkyl group having 1 to 4 carbon atoms, and R, X, n and Y have the same meanings as described above.)

That is, the cycloalkenyltriazole derivative of the present invention represented by the general formula [1] includes the N-acylimide ester or N-acylimide thiol ester derivative represented by the general formula [2] and the general formula It can be obtained by reacting the hydrazine derivative represented by [3] with an inert solvent.

Any inert solvent can be used so long as it does not inhibit the reaction, for example, alcohols such as methanol and ethanol; ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme; pentane, hexane, petroleum ether and the like. Aliphatic hydrocarbons of dichloromethane, dichloroethane, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride; Nitriles such as acetonitrile; Aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide; Water; Use of mixed solvents in which solvents selected from these are combined You can

The amount of the reaction reagent to be used is usually 1 mole of the compound of the general formula [2] and the general formula [3].
It is preferable to use 1.0 to 5.0 times the molar amount of the compound.
The reaction temperature is arbitrary between 0 ° C. and the boiling point of the solvent, but the reaction is preferably carried out in the range of 0-50 ° C. The reaction time varies depending on the reaction reagents and products, but is usually 1 to 72.
You can reach that goal in time. Specific examples of this reaction include, for example, Synthesis, 4th
83 (1983).

The compound of the general formula [2] as a raw material can be produced according to the following production method <B>. Manufacturing method <B>

[Chemical 4] (In the formula, the derivative represented by the general formula [4] may be an acid addition salt (for example, a salt with boron tetrafluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.). W represents a halogen atom,
X, n, Y, A and B have the same meanings as described above. }

That is, the compound of the general formula [2] is
It can be obtained by reacting the compounds represented by the above general formulas [4] and [5] in the presence of a base in an inert solvent. As the base, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide; diethylamine, triethylamine, pyridine,
An organic base such as 4-N, N-dimethylaminopyridine can be used.

Inert solvents that can be used include ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme; aromatic hydrocarbons such as benzene, toluene and chlorobenzene; pentane, hexane and the like. Aliphatic hydrocarbons of petroleum ethers; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride; nitriles such as acetonitrile; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide; these A mixed solvent in which solvents selected from the above are combined can be used.

The amount of the reaction reagent used is usually 1 mole of the compound of the general formula [4] and the amount of the general formula [5].
It is preferable to use 0.8 to 1.3 times the molar amount of the derivative represented by. The amount of the base used is preferably 1.0 to 2.0 times equivalent to 1 mol of the compound of the general formula [4].

The reaction time varies depending on the reaction reagent, product, etc., but is usually preferably 1 to 24 hours. The reaction temperature is preferably between 0 ° C. and the boiling point of the solvent.
A specific example of this reaction is, for example, The Journal of Organic Chemistry (J. Org. Chem.).
33, p. 1679 (1968) and the like.

The cycloalkenyltriazole derivative of the present invention shows a high preventive control effect against important diseases such as rice blight and blast without adversely affecting crops and is excellent against pests. It also has an insecticidal and acaricidal action, and also has an excellent ovicidal action against pest eggs. Therefore, the cycloalkenyltriazole derivative of the present invention is useful as a pest control agent, particularly as a pest control agent for agricultural and horticultural use such as a control agent for rice blight and blast, an insecticide, and acaricide.

The pest control agent of the present invention contains the cycloalkenyltriazole derivative represented by the general formula [1] as an active ingredient. In order to use the cycloalkenyltriazole derivative of the present invention as a pest control agent, the cycloalkenyltriazole derivative of the present invention may be used by itself, but it is a carrier, a surfactant or a dispersant generally used for formulation. Alternatively, an auxiliary agent or the like may be blended to prepare a powder, a wettable powder, an emulsion, a fine granule, a granule or the like for use.

The carrier used for formulation is
Examples thereof include solid carriers such as dichrite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate and urea; liquid carriers such as isopropyl alcohol, xylene, cyclohexane and methylnaphthalene. Surfactants and dispersants include alkylbenzene sulfonic acid metal salts, dinaphthylmethane disulfonic acid metal salts, alcohol sulfate ester salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryls. Examples thereof include ether and polyoxyethylene sorbitan monoalkylate. Examples of the auxiliary agent include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like.
At the time of use, wettable powders, emulsions, etc. are diluted to an appropriate concentration and then sprayed, while powders, fine granules, granules, etc. are directly applied.

The pest control agent of the present invention can be used by foliage spraying, soil application, nursery box application or water surface application. The mixing ratio of the active ingredient is appropriately selected as necessary, but when it is a powder or granule, it is 0.05.
~ 20% (weight), preferably 0.1-10% (weight)
It is preferable to appropriately select from the range. When used as an emulsion or wettable powder, 0.5 to 80% (weight), preferably 1 to 60%
It is preferable to appropriately select from the range of (weight).

The application rate of the pest control agent of the present invention depends on the type of compound used, the target pest, the tendency of occurrence, the degree of damage,
Although it depends on the environmental conditions, the dosage form used, etc., when used as it is, such as powder and granules, it is appropriately selected from the range of 0.05 g to 5 kg, preferably 0.1 g to 1 kg per 10 are as an active ingredient. Is good. Also,
When used in a liquid state such as an emulsion and a wettable powder, it is 0.1 to 5000 ppm, preferably 1 to 100 ppm.
It is preferable to appropriately select from the range of 0 ppm. The pest control agent of the present invention can also be used by mixing with other insecticides, fungicides, fertilizers, plant growth regulators and the like.

The insect pests to be killed and killed include planthoppers such as brown planthoppers, white-tailed planthoppers, and planthoppers; leafhoppers such as leafhoppers, green leafhoppers and aphids; aphids such as cotton aphid, green peach aphid and radish aphid; whitefly whitefly. And other whiteflies; scale insects such as stag beetle scales and stink bugs such as spider bugs; hemiptera pests such as diamondback moth, Pleurotus spp. Coleoptera insect pests such as adzuki bean weevils and urchin beetles; insect insects such as orthoptera insects such as American cockroaches and German cockroaches, and spider mites such as spider mites, kanzawa mites and citrus mites.

Among them, they have extremely excellent insecticidal and ovicidal activity against spider mites such as scab spider mites, kanzawa mites, citrus spider mites, and aphids such as cotton aphid, green peach aphid, and radish aphid. Further, the pest control agent of the present invention has a high preventive control effect against rice blight, blast and the like.

[0031]

EXAMPLES Next, the production method, formulation method and use of the cycloalkenyltriazole derivative of the present invention will be specifically described with reference to examples. Production Example 1 (Compound (4)) 5- (β-chloro-1-cyclohexenyl) -3- (2
-Chlorophenyl) -1-methyl-1H-1,2,4-
Production of triazole Methyl 2-chlorobenzthiol imidate hydroiodide (2.2 g), triethylamine (1.5 g)
Was dissolved in tetrahydrofuran (50 ml), and β-chloro-1-cyclohexenecarbonyl chloride (1.3 g) was added dropwise with stirring at 5 to 10 ° C. The mixture was stirred at room temperature for 1 hour and further stirred at room temperature overnight to react. After completion of the reaction, toluene (200 ml) was added and dissolved, washed with water, and the toluene layer was dried over anhydrous magnesium sulfate. After concentration, the product was subjected to silica gel column chromatography (trademark Wakogel C-200) to obtain 2.1 g of an intermediate imide.
Was obtained in a yield of 92.5%.

The obtained imide (1.3 g) was dissolved in toluene (50 ml), monomethylhydrazine (0.3 g) was added, and the mixture was reacted at room temperature for 24 hours. After completion of the reaction, toluene (200 ml) was added and washed with water, the toluene layer was dried over anhydrous magnesium sulfate, and after concentration, silica gel column chromatography (Wako Gel C described above using a hexane-ethyl acetate (25: 1) mixed solution as a developing solvent. -200), and the target compound 1.23 as colorless granular crystals.
g (melting point = 69-72 ° C.) were obtained with a yield of 40.7%. The NMR data of the obtained compound are shown below.

NMR data (60 MHz, CDCl ₃ solvent, δ value) 1.7 to 2.1 ppm (4H, m) 2.2 to 2.6 ppm (4H, m) 3.8 ppm (3H, s) 7. 1-8.1ppm (4H, m)

Production Examples 2 to 10 In the same manner as in Production Example 1, the compounds (1), (3), (5) to (7), (12) and (1 shown in Tables 1 to 3 above were used.
3), (15) and (19) were produced.

Next, the formulation method will be specifically described with reference to typical formulation examples. The kinds and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description, “%” in each formulation indicates a weight percentage.

Formulation Example 1 Emulsion Compound (4) 30%, cyclohexanone 20%, polyoxyethylene alkylaryl ether 11%, calcium alkylbenzene sulfonate 4% and methylnaphthalene 35% are uniformly dissolved to obtain an emulsion.

Formulation Example 2 Wettable powder Compound (13) 40%, diatomaceous earth 15%, clay 15%,
White carbon 25%, sodium dinaphthylmethane disulfonate 2% and sodium ligninsulfonate 3% are uniformly mixed and ground to obtain a wettable powder.

Formulation Example 3 Dust Powder 2% of compound (6), 5% of diatomaceous earth and 93% of clay are uniformly mixed and pulverized to give a powder.

Formulation Example 4 Granules Compound (1) 5%, lauryl alcohol sulfate sodium salt 2%, sodium ligninsulfonate 5
%, Carboxymethylcellulose 2% and clay 86
% Uniformly mix and grind. 20 parts by weight of water was added to 100 parts by weight of this mixture, and the mixture was kneaded.
After being processed into particles of ˜32 mesh, it is dried to obtain granules.

Next, the effect of the pest control agent of the present invention will be described with reference to test examples. In addition, comparative drug A ~
As D, the following compounds described in JP-A-56-154464 were prepared and used in the same manner as the test compound.

Comparative drug A: 3- (2-chlorophenyl)
-5-cyclohexyl-1-methyl-1H-1,2,4
-Triazole

[Chemical 5] Comparative drug B: 3- (2-chlorophenyl) -5-ethyl-1-methyl-1H-1,2,4-triazole

[Chemical 6] Comparative drug C: 3- (2-chlorophenyl) -5- (2-
Chlorophenyl) -1-methyl-1H-1,2,4-triazole

[Chemical 7] Comparative drug D: 3- (2-chlorophenyl) -5- (3-
Methylphenyl) -1-methyl-1H-1,2,4-triazole

[Chemical 8]

Test Example 1 Cotton aphid insecticidal test Using the compounds shown in Tables 1 to 3, a wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 100 ppm. Cucumber seedlings, which had been inoculated with cotton aphid nymphs in advance, were immersed in the drug solution and air-dried. The treated cucumber seedlings were placed in a constant temperature room at 25 ° C., and after 3 days, the number of dead insects was examined and the dead insect rate was calculated. The test was conducted in two consecutive cycles. The results are shown in Table 4.

[0043]

[Table 4]

Test Example 2 Nymphalid mite control test A wettable powder prepared according to Formulation Example 2 had an active ingredient concentration of 50.
It was diluted with water to 0 ppm. Soybean seedlings, which had been previously inoculated with 30 to 40 adults of the spider mite, were immersed in the drug solution and air-dried. 25 soybean seedlings after treatment
It was placed in a thermostatic chamber at ℃, 14 days later, the number of surviving adults was examined, and the control efficiency was calculated according to the following formula. The test was conducted in two consecutive cycles. The results are shown in Table 5.

[0045]

[Equation 1] Pest control efficiency = (1- [number of pre-treatment worms x 14-day post-treatment worm number] / [number of pre-treatment worms x non-treatment group 14]
Number of post-day insects]) x 100

[0046]

[Table 5]

Test Example 3 Nymphalid mite ovicidal test The female adult worms were released on two kidney leaf leaf discs (diameter 10 mm) to lay eggs for 24 hours, and then the female adults were removed. The wettable powder prepared according to Formulation Example 2 was diluted with water so that the concentration of the active ingredient was 20 ppm, and a certain amount was sprayed on the leaf disc leaves using a rotary spraying tower. The treated leaf disk was placed in a constant temperature room at 25 ° C., and the number of unhatched eggs was examined 7 days later, and the egg killing rate was calculated. The test was conducted in two consecutive cycles. The results are shown in Table 6.

[0048]

[Table 6]

Test Example 4 Preventive Effect Test of Rice Bacterial Blight 15 paddy rice seeds (cultivar: Kinnanfeng) were placed in a clay pot with a diameter of 7 cm.
The seeds were sown one by one and grown in a greenhouse for 4-5 weeks. A water-dispersible powder prepared according to Formulation Example 2 was diluted with water so that the active ingredient concentration was 500 ppm, and the rice seedlings having the fifth leaves were spread.
10 ml was sprayed per pot. After air-drying, Rhizoctonia sol was cultivated in fir-puffin medium.
ani) was inoculated into the strain source and immediately placed in a greenhouse at 28 ° C. After 6 days, the height of the lesion formed in the leaf sheath of rice was measured, and the control value was calculated according to the following formula. The results are shown in Table 7.
It was shown to.

[0050]

[Equation 2] Control value (%) = (1- [health of lesion in treated area] /
[Health lesion height in untreated area]) × 100

[0051]

[Table 7]

[0052]

INDUSTRIAL APPLICABILITY As described above, the cycloalkenyltriazole derivative of the present invention is novel and useful as a pest control agent.

Since the pesticidal composition of the present invention contains the cycloalkenyltriazole derivative as an active ingredient, it has excellent pesticidal activity.

Front page continuation (72) Inventor Takashi Yumida 1 Shioshinda, Fukuda-cho, Iwata-gun, Shizuoka 1 408, KAI Research Co., Ltd. 72) Inventor Yuyuki Yano 1809 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture (72) Norihiko Izawa 1-17-5 Aobadai, Kikugawa-cho, Ogasa-gun, Shizuoka Prefecture

Claims (2)

[Claims] 1. A general formula [1]: (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, a methyl group, a nitro group, a cyano group or a trifluoromethyl group, and n represents an integer of 1 to 4. Y
Represents a β-chloro-1-cycloalkenyl group having 5 to 15 carbon atoms. Here, the cycloalkenyl group of Y has 1 to 1 carbon atoms.
It may be substituted with an alkyl group of 4. ) A cycloalkenyltriazole derivative represented by: 2. A pest control agent comprising the cycloalkenyltriazole derivative according to claim 1 as an active ingredient.