JPH06157469A - Pyrazole carbonyl urea derivative, its manufacturing method and pest control agent - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a pyrazole carbonyl urea derivative having pest control activity. A pyrazole carbonyl urea derivative represented by the general formula (I), a method for producing the same, and a pest control agent containing the novel pyrazole carbonyl urea derivative represented by the formula (I) as an active ingredient. (In the formula, R represents a halogen atom, a lower alkyl group, a nitro group or a lower haloalkyl group; n represents 1 or 2;
When n is 2, R can form a 5-membered ring fused to a pyrazole ring; X represents O or S; Q represents a substituted phenyl group. [Effect] The pyrazole carbonyl urea derivative of the formula (I) is useful as an insecticide, acaricide, fungicide and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pyrazole carbonyl urea derivative which is useful as a pest control agent for insecticides, acaricides, fungicides and the like, and a process for producing the same.

[0002]

Description of the Prior Art The pyrazole carbonyl isocyanate derivative of the present invention is a novel compound, and the pyrazole carbonyl urea derivative synthesized using this compound is also a novel compound. Therefore, the pest control activity of the pyrazole carbonyl urea derivative was not known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyrazole carbonyl urea derivative, a process for producing it using a novel synthetic raw material, and a pest control agent containing the same as an active ingredient.

[0004]

As a result of research for solving the above-mentioned problems, the present inventors have found that a novel pyrazole carbonyl urea derivative has a remarkable controlling activity against pests, and The invention was completed.
That is, the present invention is as follows. A first invention is a compound (I) represented by the following formula:

[0005]

[Chemical 4]

(Wherein R represents a halogen atom, a lower alkyl group, a nitro group or a lower haloalkyl group; n represents 1 or 2; or, when n is 2, R is fused to a pyrazole ring. Can form a membered ring; X is O or S
Represents Q; represents a substituted phenyl group. ) Related to the pyrazole carbonyl urea derivative. A second invention is a compound (II) represented by the following formula:

[0007]

[Chemical 5]

(In the formula, R, n and X have the same meaning as described above.) The present invention relates to a pyrazole carbonyl isocyanate derivative. A third invention is the above-mentioned compound (II) and the following formula:

[0009]

[Chemical 6]

(In the formula, Q has the same meaning as described above.)
The present invention relates to a method for producing the above-mentioned compound (I), which comprises reacting with an aniline derivative represented by A fourth invention relates to a pest control agent containing the compound (I) as an active ingredient.

The present invention will be described in detail below. In the novel pyrazole carbonyl urea derivative [compound (I)], the novel pyrazole carbonyl isocyanate derivative [compound (II)] and the aniline derivative [compound (III)] which are raw materials for the production, substituents R, n, X and Q are as follows.

Examples of R include a halogen atom, a lower alkyl group, a nitro group and a lower haloalkyl group. Halogen atom (fluorine atom, chlorine atom, bromine atom,
The iodine atom is preferably a chlorine atom or a bromine atom. The lower alkyl group (for example, a linear or branched one having 1 to 6 carbon atoms) is preferably a linear or branched one having 1 to 4 carbon atoms; and more preferably , Methyl group, ethyl group and t-butyl group are preferred.

In the lower haloalkyl group (for example, a linear or branched one having 1 to 6 carbon atoms having a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), preferably a carbon atom A straight or branched one having a number of 1 to 4 is preferable; and a trifluoromethyl group is more preferable.

N is 1 or 2. When n is 2, R can form a 5-membered ring that is fused to the pyrazole ring.
Further, the condensed ring may have a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (the most preferable alkyl group is a methyl group. The substitution position is preferably the one described as compound 14 in Table 6.) And as the most preferable pyrazole condensed ring, those described as the compounds 13 and 14 in Table 6 can be mentioned.

Examples of the substitution position of R include the 3,4,5 position and the like, but preferably the 4 position or 3 and 4 positions.
Rank is preferred. Examples of X include O and S. Examples of Q include a substituted phenyl group.

The substituent of the substituted phenyl group Q is not particularly limited, and examples thereof include a pyridyloxy group, a halogen atom, a lower haloalkoxy group, a lower alkyl group, a nitro group, a ureido group and an aminooxymethyl group. it can.

Details of these substituents are as follows. The pyridyloxy group includes a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a chlorine atom is preferable), a halo lower alkyl group (for example, a carbon atom described as R). Examples thereof include linear or branched ones having 1 to 6 atoms; preferably a trifluoromethyl group.) As a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; preferably a chlorine atom and a fluorine atom.
Examples of the lower haloalkoxy group include a fluorine atom,
A straight or branched one having 1 to 6 carbon atoms having a halogen atom such as a chlorine atom, a bromine atom or an iodine atom (the halogen atom is preferably a chlorine atom or a fluorine atom). Preferably having 1 to 4 carbon atoms; more preferably -OC
F ₂ CHFCl is preferred.

Examples of the lower alkyl group include linear or branched ones having 1 to 6 carbon atoms; preferably those having 1 to 4 carbon atoms;
More preferably, it is an i-propyl group.

Examples of the ureido group include those described as the substituted phenyl group Q of the compound 19 shown in Table 7.

As the aminooxymethyl group, for example,
The thing described as the substituted phenyl group Q of the compound 21 shown in Table 7 can be mentioned.

The substituted phenyl group Q is not particularly limited, and examples thereof include the substituents (pyridyloxy group,
A halogen atom, a lower haloalkoxy group, a lower alkyl group, a nitro group, a ureido group, an aminooxymethyl group, etc.) can be mentioned; preferably, they are shown as Q _{1 to} Q ₂₀ in Table 1. Better; more preferably Q ₁ , Q ₆ , Q ₇ , Q ₈ ,
_{Q 9, Q 13, Q 18} , Q 19, Q 20 is good.

[0023]

[Table 1]

The substitution position of the -CONHCONHQ group to the pyrazole is preferably the 3-position, 4-position or 5-position. The compound (I) can be usually synthesized by reacting the starting compound (II) with the compound (III) in a solvent as shown below.

[0025]

[Chemical 7]

(In the formula, R, n, X and Q have the same meanings as described above.) The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, toluene and xylene. Chlorinated or non-aromatic, aliphatic such as methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane,
Alicyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; ketones such as acetone, methyl ethyl ketone, etc .; alcohols such as methanol, ethanol, ethylene glycol, etc., or hydrates thereof; N, Amides such as N-dimethylformamide, N, N-dimethylacetamide and the like; organic bases such as triethylamine, pyridine, N, N-dimethylaniline and the like; 1,3-dimethyl-2
-Imidazolidinone; dimethyl sulfoxide; a mixture of the above solvents, and the like.

The amount of the solvent used is the compound (I
The compound (II) can be used in a concentration range of 5 to 80% by weight; preferably, the compound (II) is used in a concentration of 10 to 70% by weight.

The reaction temperature is not particularly limited, but is usually within the temperature range from room temperature to the boiling point of the solvent used or less.
The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 0.3 to 24 hours.

The amount of the raw material compound (III) used is the compound (I
The compound (III) is used in an amount of 0.5 to 2 times mol, preferably 0.8 to 1.5 times mol, of I).

The novel compound (II) used in the present invention can be produced by the same method as the method for producing a benzoyl isocyanate derivative as shown below. [When X = O] For example, as shown below, J. Or
g. Chem. , 28, page 1805 (1963), etc., and can be produced from the corresponding pyrazole carboxamide.

[0031]

[Chemical 8]

(In the formula, R and n have the same meanings as described above.) [When X = S] For example, as shown below, J. Ame
r. Chem. Soc. , 61, 632 (1939
, Etc., and the like, and can be produced by reacting pyrazole carbonyl chloride with potassium thiocyanate.

[0033]

[Chemical 9]

After the completion of the reaction, the produced novel compound (II) is subjected to usual post-treatments such as extraction, concentration and filtration, and if necessary purified by a known means such as recrystallization and various chromatography. can do. Examples of the compound (II) include the compounds (II) shown in Tables 2 to 3 [compounds (II) ₁ to (II) _{16 and the} like. ] Can be mentioned.

[0035]

[Table 2]

[0036]

[Table 3]

The compound (III) used in the present invention can be produced according to a known method. For example, the substituted phenyl group Q represented by Q ₁₈ is disclosed in JP-A-59-17624.
It can be synthesized as follows according to the method described in JP-A-2.

[0038]

[Chemical 10]

As the compound (III), for example, each compound (III) [compound (III) _1- (II) consisting of the kinds of substituents corresponding to the compounds 1-24 shown in Tables 4-7 below.
I) Called ₂₄ . For example, the compound (III) ₁ means that Q in the formula represented by the compound (III) is Q ₁ . ] Can be mentioned.

The desired compound (I) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after completion of the reaction, and if necessary, known methods such as recrystallization and various chromatographies. It can be appropriately purified by the above method.

Examples of the compound (I) are shown in Tables 4 to 7.
Each compound (I) [compound (I) ₁ to (I) ₂₄ is referred to as consisting of the types of substituents corresponding to compounds 1 to 24 shown therein. For example, the compound (I) ₁ means that R _{n in the} formula represented by the compound (I) is a 4-chloro group, the carbonyl group is substituted at the 5-position, and Q is Q _1. . ] Can be mentioned.

The pests which can be controlled by the compound (I) include agricultural and horticultural pests [eg, Hemiptera (Plants, leafhoppers, aphids, whiteflies, etc.),
Lepidoptera (Beetle beetles, diamondback moths, leaf beetles, diamondback moths, etc.), Coleoptera (Gem beetles, weevil, beetles, chafers, etc.) Citrus mite, etc.)], sanitary pests (eg, flies, mosquitoes, cockroaches, etc.), stored-grain pests (Euphorbiaceae, weevil, etc.), root-knot nematodes, pine wood nematodes, mite, and the like. , Agro-horticultural pathogens (eg, wheat leaf rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato epidemic, etc.).

The pest control agent of the present invention is used for remarkable insecticidal
It has acaricidal and bactericidal effects and contains at least one compound (I) as an active ingredient. Compound (I)
Can be used alone, but is usually mixed with a carrier, a surfactant, a dispersant, an auxiliary agent, etc. by a conventional method (for example, powders, emulsions, fine granules, granules, wettable powders, oily preparations). (Prepared as a composition such as a suspension or an aerosol) is preferably used.

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 carbonization. Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Surfactants and dispersants that can be used to improve the performance of the present agent such as adhesion to animals and plants, absorption, dispersion of drug, emulsification, spread, and the like include, for example, alcohol sulfates and alkyls. Examples thereof include sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like. In order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic or the like can be used as an auxiliary agent.

In the production of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in suitable combination according to the purpose.
The concentration of the active ingredient when the compound (I) of the present invention is formulated is usually 1 to 50% by weight in the case of emulsion and 0.3 in the case of powder.
25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oils, usually 0.1 to 5% by weight for aerosols. is there. These formulations can be diluted to an appropriate concentration and sprayed on plant foliage, soil, water surface of paddy field or directly applied to various applications depending on the purpose.

[0047]

EXAMPLES The present invention will be described in detail below with reference to examples and examples. It should be noted that these examples do not limit the scope of the present invention. Reference Example 1 [Synthesis of Compound (II)] (1) Synthesis of 4-chloro-1,3-dimethyl-5-pyrazolecarbonylisocyanate [Compound (II) ₄ ] 4-chloro-1,3-dimethyl-5 -Pyrazole carboxamide (0.8 g) was dissolved in toluene (10 ml) and oxalyl chloride (1 ml) was added. After heating under reflux for 2 hours, the solvent was distilled off. The obtained brown oily substance was distilled under reduced pressure to obtain the target compound as a colorless oily substance. b. p. [125-130 ° / 5mmHg]

(2) Other compounds (II) in Tables 2 and 3
Compounds (II) ₁ to (II) ₃ and (II) ₅ to (II) ₁₆ in Tables 2 and 3 were synthesized in the same manner as in the method described in Synthesis (1).

Example 1 [Synthesis of compound (I)] (1) N- (1-methyl-4-chloro-5-pyrazolecarbonyl) -N '-[3,5-dichloro-4- (3-chloro- 5-trifluoromethyl-2-pyridyloxy)
Synthesis of Phenyl] urea (Compound 1) 3,5-dichloro-4- (3, which is the starting compound (III) _1.
-Chloro-5-trifluoromethyl-2-pyridyloxy) aniline (1.9 g) was dissolved in toluene (15 ml), and 1-methyl-4-chloro-5-pyrazolecarbonylisocyanate as the starting compound (II) ₁ was dissolved. Nart (1.0
g) solution in toluene (5 ml) was gradually added, and the mixture was stirred at room temperature for 2
Stir for hours.

After the reaction, the desired compound (I) was extracted from this reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wako Gel C-2
00, toluene: ethyl acetate = 8: 1 elution),
The obtained crystals were washed with hexane. 1.6 g of the target compound was obtained as colorless crystals.

(2) N- (1-methyl-4-chloro-5-
Pyrazolecarbonyl) -N '-[2-fluoro-4-
Synthesis of (2-chloro-1,1,2-trifluoroethoxy) phenyl] urea (Compound 3) 2-Fluoro-4- (2-chloro-1,1,2-trifluoro, which is the starting compound (III) _3. -Ethoxy) aniline (1.2 g) was dissolved in toluene (15 ml), and 1-methyl-4-chloro-5-pyrazolecarbonylisocyanate (1.0 g) as the starting compound (II) 1 was dissolved in toluene (5 ml). ) The solution was added slowly and stirred at room temperature for 2 hours.

After the reaction, the target compound (I) was extracted from this reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wako Gel C-2
00, toluene: ethyl acetate = 10: 1), and the obtained crystals were washed with hexane. 1.1 g of the target compound was obtained as colorless crystals.

(3) N- (4-chloro-1,3-dimethyl-5-pyrazolecarbonyl) -N '-[3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2)
- pyridyloxy) phenyl] compounds of the starting materials for synthesis urea (Compound 6) (III) is ₆ 3,5-dichloro-4- (3
-Chloro-5-trifluoromethyl-2-pyridyloxy) aniline (1 g) was dissolved in toluene (10 ml), and the starting compound (II) ₄ , 4-chloro-1,3-dimethyl-5-pyrazolecarbonylisocyanate. Nato (1.8 g) was gradually added, and the mixture was stirred at room temperature for 3 hours.
After the reaction, the solvent was distilled off under reduced pressure, and the obtained crystals were recrystallized from hexane. 1 g of the target compound was obtained as colorless crystals. (4) Other target compounds (I) in Tables 4 to 7 were synthesized in the same manner as the methods described in (1) to (3).

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

[Table 7]

Example 2 [Preparation of preparation] (1) Preparation of granules 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) Parts and soda 2 of lignin sulfonate
Part by weight was uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain a granule.

(2) Preparation of Wettable Powder 10 parts by weight of Compound 1, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neoperex Powder (trade name; manufactured by Kao Corporation) and 0.5 parts by weight of Demol (trade name; manufactured by Kao Co., Ltd.) were uniformly mixed and then 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 Kasei Co., Ltd.) were added and uniformly mixed and dissolved to obtain an emulsion.

(4) Preparation of Dust A powder was obtained by uniformly mixing 5 parts by weight of compound 1, 50 parts by weight of talc and 45 parts by weight of kaolin.

Example 3 [Efficacy test] (1) Efficacy test against Spodoptera litura Compounds (I) shown in Tables 4 to 7 prepared according to Example 2
Each of the wettable powders of 1 is diluted to 500 ppm with water containing a surfactant (0.01%), soybean soybean leaves are dipped in each of these chemical solutions for 30 seconds, put in each plastic cup one by one, and air dried. did. In each of these cups, 10 Spodoptera litura (2nd instar larvae) were released, covered, and allowed to stand in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The insecticidal effect is evaluated in four stages (A: 100%, B: 99-80%, C: 7) depending on the range of insecticidal rate.
9-60%, D: 59% or less). The results are shown in Table 8.

[0063]

[Table 8]

(2) Efficacy test against diamondback moth Compound (I) shown in Tables 4 to 7 prepared according to Example 2
30% of each wettable powder in water containing surfactant (0.01%)
After diluting to 0 ppm, cabbage leaf pieces (5 × 5 cm) were dipped in each of these chemical solutions for 30 seconds, placed in each plastic cup one by one and air dried. Next, in each of these cups, 10 diamondback moths (third instar larvae) were released, and the cups were capped.
The cup was allowed to stand 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 mortality rate. The results of evaluation of the insecticidal effect are shown in Table 9 by the four-step evaluation method described in (1) above.

[0065]

[Table 9]

(3) Control efficacy test against rice blast (preventive effect) Ten rice (cultivar: Nihonbare) was grown in a plastic flower pot with a diameter of 6 cm to give 1.5 leaf stage seedlings. The wettable powder prepared according to Example 2 from the compounds shown in Tables 4 to 7 was treated with water containing a surfactant (0.01%) to obtain 50 parts.
It diluted to 0 ppm and sprayed 20 ml per pot. After spraying, it was cultivated in a glass greenhouse for 2 days, and then a conidial suspension of rice blast fungus was prepared and sprayed uniformly on plant leaves. After inoculation, grow in a humid chamber at 28 ° C for 5 days,
The degree of rice blast lesions appearing on the leaves was investigated. The evaluation of the bactericidal effect is 6 levels (0:
The whole is affected, 1: the lesion surface is about 60%, 2: the lesion area is about 40%, 3: the lesion area is about 20%, 4: the lesion area is 10% or less, and 5: no lesion. ). The results are shown in Table 10.

[0067]

[Table 10]

(4) Control efficacy test against barley powdery mildew (preventive effect) Ten barley (cultivar: black wheat) was grown in a plastic flower pot with a diameter of 6 cm, and seedlings of 1.5 leaf stage were grown. In addition, each wettable powder of the compound (I) shown in Tables 4 to 7 prepared according to Example 2 was mixed with a surfactant (0.01%).
Each of them was sprayed with 20 ml per one pot by diluting each to 500 ppm with water containing water. These were cultivated in a glass greenhouse for 2 days, and then the barley powdery mildew fungus conidia spores were collected from the diseased leaves and sprinkled evenly over the plants to inoculate. Next, these were grown in a glass greenhouse for one week, and the degree of barley powdery mildew lesions appearing on each first leaf was investigated. The result of the evaluation of the bactericidal effect,
Table 11 shows the 6-step evaluation method described in (3) above.

[0069]

[Table 11]

[0070]

INDUSTRIAL APPLICABILITY The novel pyrazole carbonyl urea derivative of the present invention has an excellent pesticidal effect such as insecticidal, acaricidal and bactericidal effects.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical indication location C07D 213: 00 6701-4C 231: 00) 7431-4C (72) Inventor Kiyoshi Shitsuchi 1978 Ogushi, Ube, Yamaguchi Prefecture No. 5 Ube Kosan Co., Ltd. in the Ube Research Center (72) Inventor Yoshinori Yamanaka 1978, Kobe, Obe City, Ube City Yamaguchi Prefecture No. 5 No. 5 Ube Kosan Co., Ltd. in the Ube Research Center (72) Inventor Mizuzu Makoto, 1978, Koujigushi, Ube City, Yamaguchi Prefecture 5 Ube Kosan Co., Ltd. Ube Laboratory

Claims (4)

[Claims] 1. The following formula: (In the formula, R represents a halogen atom, a lower alkyl group, a nitro group or a lower haloalkyl group; n represents 1 or 2;
Alternatively, when n is 2, R is fused to the pyrazole ring 5
A member ring can be formed; X represents O or S; Q represents a substituted phenyl group. ) The pyrazole carbonyl urea derivative shown by these. 2. The following formula: (In the formula, R, n and X are as defined in claim 1.) A pyrazole carbonyl isocyanate derivative represented by the formula. 3. A pyrazole carbonyl isocyanate derivative represented by the formula (II) according to claim 2 and the following formula: (In the formula, Q has the same meaning as described in claim 1.) A method for producing a pyrazole carbonyl urea derivative represented by formula (I) according to claim 1, wherein the aniline derivative represented by formula (1) is reacted. 4. A pest control agent comprising the pyrazole carbonyl urea derivative represented by the formula (I) according to claim 1 as an active ingredient.