JP2803075B2 - Phenoxyalkylamine compounds, their preparation and pest control agents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenoxyalkylamine compound which is a pest control agent useful as an insecticide, acaricide, fungicide and the like.

[0002]

2. Description of the Prior Art Hitherto, many phenoxyalkylamine compounds have been known as pesticides. For example,
JP-A-54-17123, JP-A-55-7680
No. 3, JP-A-55-76804, quinazoline compounds, JP-A-55-108806, pyridopyrimidine compounds, JP-A-59-42387, thienopyrimidine compounds, and JP-A-59-42387. JP-A-36666, JP-A-59-366667, JP-A-61-36667.
Pyrimidine compounds are reported in 286373 and JP-A-62-67. However, a novel cyclohexa [1,2-c] -3 such as the compound of the present invention is used.
-No report has been made on pyrazolecarboxamide compounds. Therefore, it is not known to have a pesticidal activity which is useful as an insecticide, acaricide, fungicide and the like.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel phenoxyalkylamine compound, a process for producing the same, and a pesticidal composition which is useful as an insecticide, acaricide, fungicide and the like. That is.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a novel phenoxyalkylamine compound is useful as a pesticide, acaricide, fungicide and the like. The present inventors have found that they have a remarkable controlling activity as a controlling agent, and have completed the present invention. That is, the present invention is as follows. The first invention provides the following formula (I):

[0005]

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[In the formula, R ¹ represents a lower alkyl group or a lower haloalkyl group; R ² represents a hydrogen atom, a lower alkyl group or a halogen atom; R ³ represents a lower alkenyl group or —A—O—R ⁵ ( Wherein A represents a lower alkylene group;
R ⁵ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group. ) Represents; R ⁴ represents a hydrogen atom, a lower alkyl group or a halogen atom. And a phenoxyalkylamine compound represented by the formula: A second invention provides the following formula (II):

[0007]

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(Wherein R ¹ has the same meaning as described above;
X represents a halogen atom. And a cyclohexa [1,2-c] -3-pyrazolecarboxylic acid compound represented by the following formula (III):

[0009]

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(Wherein R ² , R ³ and R ⁴ have the same meanings as described above), and are reacted with a phenoxyalkylamine represented by the formula (I). The present invention relates to a method for producing an alkylamine compound. The third invention relates to an insecticide / acaricide and a fungicide containing the phenoxyalkylamine compound represented by the above formula (I) as an active ingredient.

Hereinafter, the present invention will be described in detail. Novel phenoxyalkylamine compounds (I) which are the above-mentioned target compounds, and (II) and (II
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X in I) are as follows.

R ¹ is a linear or branched lower alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl). -Butyl group, t-butyl group, etc.), having 1 carbon atom
To 4 linear or branched lower haloalkyl groups (for example, trifluoromethyl group, difluoromethyl group,
Fluoroethyl group, 2-chloroethyl group, 2,2,2-
Trifluoroethyl group, 3,3,3-trifluoropropyl group), and a methyl group is preferable.

R ² is a hydrogen atom or a group having 1 to 1 carbon atoms.
4 linear or branched lower alkyl groups (for example, R ¹
And a halogen atom (eg, a chlorine atom, an iodine atom, a bromine atom, a fluorine atom, etc.), and a methyl group is preferred.

As R ³ , a linear or branched lower alkenyl group having 3 to 5 carbon atoms (for example, allyl group, 1
-Butenyl group, 2-butenyl group, 1-methylallyl group,
2-methylallyl, 2-pentenyl group, etc. isoprenyl ^{group), - A-O-R} 5 [Note, A is 1 to carbon atoms
4 linear or branched lower alkylene group (e.g., methylene group, ethylene group, propylene group, butylene group) represents; the R ^5, 1 to 4 carbon atoms, straight or branched A lower alkyl group (for example, a lower alkyl group described above as R ¹ ), a linear or branched lower alkenyl group having 3 to 5 carbon atoms (for example, an allyl group, 1-butenyl group, 2- A butenyl group, a 1-methylallyl group, a 2-methylallyl group, a 2-pentenyl group, an isoprenyl group, etc.), a linear or branched lower alkynyl group having 3 to 4 carbon atoms (for example, a 1-propynyl group, 2-
A propynyl group, a 2-butynyl group, etc.).
-Ethoxytoethyl groups and the like are preferred.

R ⁴ is a hydrogen atom or a group having 1 to 1 carbon atoms.
4 linear or branched lower alkyl groups (for example, R ¹
And a halogen atom (for example, a chlorine atom, an iodine atom, a bromine atom, a fluorine atom, etc.), and a methyl group is preferable. Further, when R ⁴ is other than a hydrogen atom, the substitution position is preferably the 3-position or the 6-position. As X,
Examples include a halogen atom (for example, a chlorine atom, an iodine atom, a bromine atom, a fluorine atom, and the like).

The compound (I) of the present invention can be synthesized by the following method. Compound (I) of the present invention
The synthesis of the compound (I) is usually carried out as shown below.
The reaction can be carried out by reacting I) with compound (III) in a solvent or in the absence of a solvent. In order to accelerate the reaction, the reaction is preferably carried out in the presence of a base.

[0017]

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(Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above). The solvent is not particularly limited as long as it does not directly participate in the reaction. Chlorinated or non-chlorinated aromatics, such as, toluene, xylene, methyl naphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane,
Aliphatic or alicyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane and the like;
Ketones such as acetone and methyl ethyl ketone;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide; organic bases such as triethylamine, pyridine, N, N-dimethylaniline; 1,3-dimethyl-2-imidazolidinone; dimethyl Sulfoxides; and mixtures of the above-mentioned solvents.

The amount of the solvent used depends on the amount of the compound (I
The compound (II) can be used in such a manner that the concentration of I) is in the range of 5 to 80% by weight.
Is preferably used in such a manner that the concentration thereof becomes 10 to 70% by weight.

The base is not particularly limited.
Organic bases such as triethylamine, pyridine, N, N-dimethylaniline, DBU, etc .; alkali metal alkoxides such as sodium methoxide, sodium ethoxide; sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate , Sodium hydrogencarbonate, potassium carbonate, and the like, but triethylamine, pyridine, N, N
-Organic bases such as dimethylaniline, DBU and the like are preferred.

The compound can be used in a molar amount of 0.001 to 5 times, preferably 0.8 to 1.5 times the molar amount of the compound (II).

The reaction temperature is not particularly limited, but is in a temperature range from the ice-cooling temperature to the boiling point of the solvent used,
C. to 10C. Are preferred. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 0.3 to 2 hours.

The amount of the starting compound used is 0.5 to 2 times the molar amount of the compound (III) with respect to the compound (II).
Preferably it is 0.8 to 1.5 times mol.

The compound (II) used in the present invention is described, for example, in Ann. Chem. , 536, 97 (1938), etc., and can be easily produced using 2-ketocyclohexylglyogicalic acid esters and hydrazines.

Compound (III) used in the present invention can be easily produced by a method known per se shown by the following formula.

[0026]

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(Wherein, R ² , R ³ , R ⁴ and X have the same meanings as described above, and Y represents a leaving group.) As the leaving group, halogen atoms such as chlorine and bromine; Alkanesulfonic acid residues, arylsulfonic acid residues and the like can be mentioned. As the compound (III), for example, Tables 1-4
Each compound (III) [compound (III) _1- (I
II) Called ₃₀ . [For example, the compound (III) corresponding to the compound 1 is replaced with the compound (I
II) Called ₁ . The compound (III) ₁ means that R ^{2 in the} formula represented by the compound (III) is a methyl group, R ³ is an allyl group, and R ⁴ is a hydrogen atom. ].

After completion of the reaction, the target compound (I) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, filtration and the like, and if necessary, recrystallization, various chromatographic techniques and the like. Can be appropriately purified by the above-mentioned means.

As the compound (I), for example, Tables 1 to 4
[For example, compound 1 is R in the formula represented by compound (I).
¹ and R ² represent a methyl group, R ³ represents an allyl group, and R ⁴ represents a hydrogen atom. ].

The pests which can be controlled by the compound (I) of the present invention include agricultural and horticultural pests [for example, Hemiptera (hoppers, leafhoppers, aphids, whiteflies, etc.) and lepidoptera (weevils, etc.). , Scarabaeidae, Coleoptera, Pestiformes, Scarabaeidae, Pieris beetle, etc., Coleoptera (Tenebrionidae, Weevils, Chrysomelidae, Scarabaeidae, etc.), Acari (Acari: Tetranychidae, Tetranychidae, etc.) )], Sanitary pests (for example, flies, mosquitoes, cockroaches, etc.), stored grain pests (e. G. For example, wheat leaf rust, barley powdery mildew, cucumber downy mildew, rice blast, toma Epidemics, etc.) can be mentioned.

The phenoxyalkylamine compound as the pesticidal agent of the present invention has a remarkable insecticidal, acaricidal and fungicidal effect and contains at least one compound (I) as an active ingredient. . The compound (I) can be used alone, but it is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent and the like (for example, powder, emulsion, fine granule, granule, hydrate) by an ordinary method. Agents, oily suspensions, aerosols and the like).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbon Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene, etc.) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Examples of surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement of absorption, dispersion, emulsification and spreading of drugs, include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in an appropriate combination according to the respective purposes.
When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in the emulsion, and usually from 0.3 to 0.3 in the powder.
25 to 25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. is there.

These preparations can be used for various purposes by diluting them to an appropriate concentration and spraying them on the foliage of plants, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.
Note that these examples do not limit the scope of the present invention. Example 1 [Synthesis of Compound (I)]

(1) Synthesis of N- [2- (4-allyl-2-methylphenoxy) ethyl] -2-methyl-cyclohexa [1,2-c] -3-pyrazolecarboxamide (compound 1) 2-methyl -Cyclohexa [1,2-c] -3-pyrazolecarboxylic acid (1.45 g) was converted to thionyl chloride (2.5
under reflux for 3 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain 2-methyl-cyclohexa [1,2-c] -3-pyrazolecarboxylic acid chloride. This was dissolved in toluene (10 ml),
The mixture was added dropwise to a solution of (4-allyl-2-methylphenoxy) ethylamine (2.0 g) and triethylamine (1.2 g) in toluene (10 ml) with stirring under ice-cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to complete the reaction. Then water was added and extracted with toluene. The extract was washed with 1N-sodium hydroxide and further washed with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue is subjected to silica gel column chromatography (Wakogel C-20).
0, toluene: ethyl acetate = 9: 1) to give 1.4 g of the desired product.

(2) N- {2- [4- (2-ethoxyethyl) -2-methylphenoxy] ethyl} -2-methyl-cyclohexa [1,2-c] -3-pyrazolecarboxamide (compound 3) Synthesis of 2-methyl-cyclohexa [1,2-c] -3-pyrazolecarboxylic acid (1.45 g) with thionyl chloride (2.5
under reflux for 3 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain 2-methyl-cyclohexa [1,2-c] -3-pyrazolecarboxylic acid chloride. This was dissolved in toluene (20 ml),
The mixture was added dropwise to a toluene (20 ml) solution of [4- (2-ethoxyethyl) -2-methylphenoxy] ethylamine (2.3 g) and triethylamine (1.2 g) under ice-cooling and stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to complete the reaction. Then water was added and extracted with toluene. The extract was washed with 1N-sodium hydroxide and further washed with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 9: 1) to obtain 2.3 g of the desired product.

Example 2 [Preparation of preparation] (1) Preparation of granule 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium ligninsulfonate were uniformly mixed, then kneaded by adding a small amount of water, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 67.5 parts by weight of kaolin, 20 parts by weight of white carbon, 2 parts by weight of Neoperex powder (trade name, manufactured by Kao Corporation) and Demol (trade name) Name; manufactured by Kao Corporation)
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of Compound 1 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name, manufactured by Sanyo Chemical Industries) was added, mixed uniformly, and dissolved to obtain an emulsion. .

(4) Preparation of powder 5 parts by weight of compound 1, 50 parts by weight of talc and kaolin 4
5 parts by weight were uniformly mixed to obtain a powder. Example 3 [Efficacy test]

(1) Test for potency against leafhopper Leafhopper Compound (I) prepared according to Example 2 and shown in Tables 1-4
Is diluted to 100 ppm with water containing a surfactant (0.01%), and rice seedlings are immersed in each of these chemical solutions for 15 seconds, air-dried, and then inserted into respective glass cylinders. did. Next, ten third-instar larvae of the green leafhopper were released into each cylinder, a porous stopper was placed on the cylinder, and the tube was allowed to stand in a constant temperature room at 25 ° C. After 4 days, live and dead insects were counted to determine the mortality. The insecticidal effect was evaluated in four stages (A: 100) according to the range of the insecticidal rate.
%, B: 99-80%, C: 79-60%, D: 59%
Below). Table 5 shows the results.

[0043]

[Table 5]

(2) Efficacy test against adult female spider mite (Acari: Tetranychidae) Compound (I) shown in Tables 1-4 prepared according to Example 2
Each hydration agent in water containing a surfactant (0.01%).
Each bean leaf (20 m in diameter) diluted to 0 ppm and infested with 10 adult female spider mites in each of these solutions
m) for 15 seconds. Next, each leaf piece was left in a constant temperature room at 25 ° C., and after 3 days, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate. The results of the evaluation of the acaricidal effect were evaluated according to the four-step evaluation method described in the above (1) in Table 6.
Shown in

[0045]

[Table 6]

(3) Efficacy test for spider mite eggs Compound (I) shown in Tables 1-4 prepared according to Example 2
Each hydration agent in water containing a surfactant (0.01%).
Each bean leaf (20 m in diameter) diluted to 0 ppm and infested with 10 adult female spider mites in each of these solutions
m) for 15 seconds. Next, each of these leaf pieces was left in a constant temperature room at 25 ° C., and after 7 days, the number of unhatched eggs in each leaf piece was counted to determine the ovicidal rate. The evaluation of the ovicidal effect was performed in four stages (A: 100%, B: 99) depending on the range of the ovicidal rate.
-80%, C: 79-60%, D: 59% or less). Table 7 shows the results.

[0047]

[Table 7]

(4) Efficacy test for Conaga (Compound) Compound (I) prepared according to Example 2 and shown in Tables 1-4
Each hydration agent in water containing a surfactant (0.01%).
It was diluted to 0 ppm, and cabbage leaf pieces (5 × 5 cm) were immersed in each of these chemical solutions for 15 seconds, placed one by one in each plastic cup, and air-dried. Next, 10 cup moths (3rd instar larvae) were released into each of these cups, covered, and
It was left in a constant temperature room at 5 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The results of the evaluation of the insecticidal effect are shown in Table 8 using the four-step evaluation method described in the above (1).

[0049]

[Table 8]

(5) Efficacy test on brown planthopper Compound (I) shown in Tables 1-4 prepared according to Example 2
Each hydration agent in water containing a surfactant (0.01%).
After dilution to 0 ppm, 30
After immersion for 2 seconds and air-drying, it was inserted into each glass cylinder. Next, 10 third-instar brown planthoppers were released into each of these glass cylinders, covered with a porous lid, and allowed to stand in a constant temperature room at 25 ° C., and after 4 days, the number of live and dead insects in each glass cylinder was counted and the insecticidal rate was determined. I asked. The results of the evaluation of the insecticidal effect are shown in Table 9 by the four-step evaluation method described in the above (1).

[0051]

[Table 9]

(6) Test for controlling efficacy against wheat rust (preventive effect) Wheat (cultivar: Kobushi wheat) was grown 10 plants per pot in a plastic flowerpot having a diameter of 6 cm, and planted at 1.5-leaf stage. Each wettable powder of compound (I) shown in Tables 1-4 prepared according to Example 2 was added to a surfactant (0.01
%), And diluted with water to 500 ppm, and each of these chemicals was sprayed at 20 ml per pot. These two
The plants were cultivated in a glass greenhouse for a day, and then a wheat rust spore suspension (7 × 10 ⁴ spores / ml) was sprayed uniformly.
Next, these were grown for one week in a glass greenhouse, and the degree of wheat rust spots appearing on each first leaf was investigated. The evaluation of the bactericidal effect was performed in six stages (0: the whole diseased, 1: the lesion area was about 60%, 2: the lesion area was about 40%, and 3: Lesion area is about 20% 4:
(Lesion area is 10% or less, 5: no lesion). Table 10 shows the results.

[0053]

[Table 10]

[0054]

The novel phenoxyalkylamine compounds of the present invention have excellent pest control effects such as insecticidal, acaricidal and bactericidal activities.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C07D 231/54

Claims (3)

(57) [Claims] (1) The following formula: [Wherein, R ¹ represents a lower alkyl group or a lower haloalkyl group; R ² represents a hydrogen atom, a lower alkyl group or a halogen atom; R ³ represents a lower alkenyl group or —A—O—R
⁵ (however, A represents a lower alkylene group; R ⁵ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group); R ⁴ represents a hydrogen atom, a lower alkyl group or a halogen atom. A phenoxyalkylamine compound represented by the formula: 2. The following formula: (Wherein, R ¹ has the same meaning as in claim 1; X represents a halogen atom.)
c] -3-Pyrazolecarboxylic acid compound and the following formula: (Wherein R ² , R ³ and R ⁴ have the same meanings as in claim 1), and are reacted with phenoxyalkylamines represented by the formula (I). A method for producing the phenoxyalkylamine compound shown. 3. A pest control agent comprising a phenoxyalkylamine compound represented by the formula (I) according to claim 1 as an active ingredient.