JP2000290105A - Benzhydroxymoylazole compound and herbicide containing the same as active ingredient - Google Patents

Abstract

(57) [Problem] To provide a herbicide characterized by containing a benzhydroxymoylazole compound as an active ingredient. SOLUTION: The herbicide of the present invention has the following formula (1): (Wherein R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms;
³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ⁴ is an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms having an alkoxycarbonyl group having 2 to 5 carbon atoms. Alkyl group, benzyl group, 2-5 carbon atoms
X represents an alkylcarbonyl group, a pyrimidyl group, a carbamoyl group having 2 to 5 carbon atoms, or a pyridyl group;
Represents CH and N. ) Is contained as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a benzhydroxymoylazole compound and a herbicide containing the compound as an active ingredient.

[0002]

2. Description of the Related Art Benzhydroxymoylazole compounds are disclosed in JP-A-1-308260 and JP-A-3-685.
No. 59, JP-A-5-33111, JP-A-5-331
012, JP-A-6-41086, JP-A-6-145
No. 151, JP-A-10-7659 and WO92 / 09
No. 581 describes an insecticidal activity. However, no herbicidal activity is described. Also, a benzhydroxymoylazole compound having an alkyl group at the 2,6-positions at the same time is a novel compound, and its biological activity has not been known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a benzhydroxymoylazole compound and a herbicide containing the same as an active ingredient.

[0004]

Means for Solving the Problems The present inventors have studied to solve the above-mentioned problems, and as a result, have found that a drug containing a benzhydroxymoylazole compound as an active ingredient has an excellent herbicidal effect. Completed the invention. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0005]

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Wherein R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms; R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ represents an alkyl group having 1 to 4 carbon atoms, an benzyl group, an alkyl group having 2 to 5 carbon atoms, which is unsubstituted or has an alkoxycarbonyl group having 2 to 5 carbon atoms as a substituent; A carbonyl group, a pyrimidyl group, a carbamoyl group having 2 to 5 carbon atoms, or a pyridyl group; X represents CH or N). It relates to herbicides.

According to a second aspect of the present invention, R ¹ and R ² represented by the above formula (1) each independently have 1 to 1 carbon atoms.
It relates to a benzhydroxymoylazole compound which is four alkyl groups.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The compound represented by the formula (1) [hereinafter, the compound corresponding to the formula (1) may be referred to as a compound (1). R ^{1 to} R ⁴ and X are as follows.

[R ¹ and R ² ] R ¹ and R ² each independently include a halogen atom and an alkyl group having 1 to 4 carbon atoms. As a halogen atom,
Examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; preferably a chlorine atom. Alkyl groups can include straight or branched ones; preferably a methyl group.

[R ³ ] Examples of R ³ include a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Alkyl groups can include straight or branched ones; preferably a methyl group.

[R^Four] R^FourAs unsubstituted or substituted
An alkoxycarbonyl group having 2 to 5 carbon atoms
An alkyl group having 1 to 4 carbon atoms having benzyl, benzyl
Group, an alkylcarbonyl group having 2 to 5 carbon atoms,
Midyl group, carbamoyl group having 2 to 5 carbon atoms, pyri
Jil groups can be mentioned. (1) unsubstituted or substituted with 2 to 5 carbon atoms
An alkoxycarbonyl group having 1 to 4 carbon atoms
In the alkyl group, as the unsubstituted alkyl group,
Chain or branched, for example CH_Three, C_TwoH_Five, I-
C_ThreeH₇, N-C_ThreeH ₇, Sec-C_FourH₉To name
Can be. As the substituted alkyl group, straight-chain or branched
But preferably: CH_Two
It is. Alkoxycarbonyl group having 2 to 5 carbon atoms
Is a compound having a linear or branched alkoxy group.
A carbonyl group; preferably
The oxy group is OCH_ThreeIt is.

(2) Examples of the benzyl group include those having an unsubstituted or substituted group. (3) Examples of the alkylcarbonyl group having 2 to 5 carbon atoms include a carbonyl group having a linear or branched alkyl group.
H ³ . (4) Examples of the pyrimidyl group include those that are unsubstituted or have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. Halogen atoms include fluorine, chlorine, bromine,
Mention may be made of iodine atoms; preferably they are chlorine atoms. Alkyl groups can include straight or branched ones; preferably an ethyl group. Alkoxy groups can include straight or branched ones; preferably methoxy groups.

(5) The carbamoyl group having 2 to 5 carbon atoms; preferably -CONHCH ₃ . (6) Examples of the pyridyl group include those having an unsubstituted or substituted group. Examples of the substituent include a halogen atom and a haloalkyl group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; preferably a chlorine atom. The haloalkyl group, there may be mentioned a straight or branched; preferably, is CF _3.

[X] Examples of X include CH and N. Compound (1) of the present invention is, for example, a sulfate,
Since salts such as hydrochloride, nitrate and phosphate can be formed, those salts are also included in the present invention. Also,
Since the compound (1) has geometrical isomers of E-form and Z-form, the present invention includes these isomers and mixtures thereof.

As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned. From the viewpoint of drug efficacy, the following compounds are preferred. (1) R ^{1 to} R ³ are an alkyl group having 1 to 4 carbon atoms, and R ⁴ is unsubstituted or 2 to 2 carbon atoms as a substituent.
1 to 5 carbon atoms having 5 alkoxycarbonyl groups
Compound (1) which is four alkyl groups and X is N.
For example, compounds 1, 2, 8 described in Table 1 can be exemplified. (2) R ^{1 to} R ³ are an alkyl group having 1 to 4 carbon atoms, and R ⁴ is unsubstituted or 2 carbon atoms as a substituent.
1 carbon atom having up to 5 alkoxycarbonyl groups
A compound (1) wherein the compound is (1) to (4) alkyl groups and X is CH. For example, compound 9 described in Table 1 can be exemplified.

(3) R ¹ and R ² are halogen atoms,
A compound wherein R ³ is a hydrogen atom, R ⁴ is an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms having an alkoxycarbonyl group having 2 to 5 carbon atoms, and X is N 1). For example, Compound 12, described in Table 1,
13 and the like. (4) R ¹ and R ² are halogen atoms, R ³ is a hydrogen atom, and R ⁴ is unsubstituted or has 1 to 4 carbon atoms having an alkoxycarbonyl group having 2 to 5 carbon atoms as a substituent. (1) wherein X is CH. For example, Compound 14 described in Table 1 can be exemplified.

[Production method of compound (1)]
As shown below, it can be produced by reacting compound (2) with compound (3) without solvent or in a solvent, if necessary in the presence of a base.

[0018]

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(Wherein, R ^{1 to} R ⁴ and X have the same meanings as described above; Z represents a leaving group such as a halogen atom or a mesyl group). Chem. Res. , Syn
op. (1987), Issue 7, 240, by reacting the corresponding benzonitrile oxides with azoles. Alternatively, it can be produced by reacting a corresponding benzohydroxymoyl halide with an azole according to the method described in JP-A-1-308260. Starting compound (3) can be obtained commercially or by a known synthesis method.

The solvent used in the synthesis of compound (1) is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include diethyl ether, tetrahydrofuran,
Ethers such as dioxane; dipolar aprotic solvents such as N, N-dimethylformamide and dimethylsulfoxide; aromatic hydrocarbons such as benzene, toluene and xylene; nitriles such as acetonitrile; be able to. The base used for the production of the compound (1) includes alkali carbonates such as potassium carbonate and sodium carbonate; sodium methoxide;
Alkali alkoxides such as potassium-t-butoxide; inorganic bases such as sodium hydride;

The method for producing the compound (1) has a reaction concentration of 2 to 2.
80%. In the production method, the ratio of using a base is 0.5 to 2 with respect to 1 mol of the compound (1).
It can be added in a molar ratio, but preferably in the range of 1-1.
2 mol is good. The reaction temperature is not particularly limited as long as the reaction is performed at a temperature equal to or lower than the boiling point of the solvent to be used. The reaction time varies depending on the above-mentioned concentration and temperature, but can be usually 0.5 to 24 hours.

The herbicide of the present invention contains at least one compound (1) as an active ingredient. The herbicide of the present invention is effective for weeds such as monocotyledonous weeds and dicotyledonous weeds, and can be used as a herbicide for paddy fields and field crops. As monocotyledon weeds, Nobie, Firefly,
Spodoptera striata, Tata sedge, Heramodaka, Konagi,
Paddy field weeds such as Urikawa; and field weeds such as Meishiba, Ohishiba, Enokorogosa, Spodoptera cricket, and Spodoptera edulis. Paddy field weeds such as annual broadleaf (Azena, Kikasigusa) and seri as dicotyledonous weeds;
Upland weeds such as Shiroza, Inubiyu, Ichibai, Morning Glory, Onamomi, Ebisugusa, and Chickweed can be mentioned.
The herbicide of the present invention can be applied both before and after germination of the plant, and can be mixed with the soil before sowing. The dosage of the active compound of the present invention can be varied over a wide range depending on the kind of the compound, the kind of the target plant, the time of application, the place of application, the nature of the desired effect, and the like. The range of about 0.001 to 10 kg, preferably about 0.01 to 5 kg, of active compound per hectare can be exemplified.

The compound (1) can be used alone, but it is usually compounded with a diluent, a surfactant, a dispersant, an auxiliary agent and the like by a conventional method. Granules, wettable powders, wettable granules, aqueous suspensions, oil suspensions, emulsions, solubilized preparations, oils, microcapsules,
It is preferable to prepare and use as a composition such as an aerosol. Examples of the solid diluent include talc, bentonite, montmorillonite, clay, kaolin, calcium carbonate, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea.

Examples of the liquid diluent include hydrocarbons such as kerosene and mineral oil; aromatic hydrocarbons such as benzene, toluene, xylene, dimethylnaphthalene and phenylxylylethane; chlorinated hydrocarbons;
For example, chloroform, carbon tetrachloride and the like; ethers such as dioxane, tetrahydrofuran and the like; ketones,
For example, acetone, cyclohexanone, isophorone, etc .;
Esters such as ethyl acetate, ethylene glycol acetate, dibutyl maleate and the like; alcohols such as methanol, n-hexanol and ethylene glycol; polar solvents such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; No.

Examples of the fixing agent and the dispersing agent include casein, polyvinyl alcohol, carboxymethylcellulose, bentonite, xanthan gum and gum arabic. Aerosol propellants include, for example, air, nitrogen, carbon dioxide, propane, halogenated hydrocarbons and the like. Examples of the stabilizer include PAP, B
HT and the like. As the surfactant, for example,
Alkyl sulfate salt, alkyl sulfonate, alkyl benzene sulfonate, lignin sulfonate, dialkyl sulfosuccinate, naphthalene sulfonate condensate, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl ester, Examples thereof include an alkyl sorbitan ester, a polyoxyethylene sorbitan ester, and a polyoxyethylene alkylamine.

In the preparation of the present agent, the above-mentioned diluents, surfactants, dispersants and adjuvants can be used alone or in appropriate combination according to the respective purposes.
When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in an emulsion, and usually 0.3% in a powder.
25 to 25% by weight, usually 1 to 90 for wettable powder and wettable powder.
%, Usually 0.5 to 10% by weight for granules, usually 0.5 to 40% by weight for suspensions, usually 1 to 30% by weight for emulsions, usually 0.5 to 20% for solubilized preparations. % For aerosol, usually 0.1 to 5% by weight. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0027]

The present invention will be specifically described below with reference to examples and reference examples. Note that these examples do not limit the scope of the present invention. Reference Example [Synthesis of Starting Compound (2)] Synthesis of 1-[(2,4,6-trimethyl) benzhydroxymoyl] -1H-imidazole 2,4,6-trimethylbenzonitrile oxide (1.
5 g), imidazole (0.70 g) and potassium carbonate (1.67 g) were suspended in 25 ml of tetrahydrofuran and stirred at room temperature for 1 day. After the reaction solution was extracted with ethyl acetate, the extract was washed with water, washed with brine, dried over sodium sulfate, and concentrated. Then, hexane was added thereto to crystallize, filtered, and air-dried to obtain the desired product (1.6 g).

Example 1 Synthesis of Compound (1) (1) Synthesis of 1- [Oi-propyl- (2,4,6-trimethyl) benzhydroxymoyl] -1H-triazole (Compound 1) -[(2,4,6-trimethyl) benzhydroxymoyl] triazole (0.38 g), potassium carbonate (0.3 g) and i-propyl iodide (0.4 g)
Was suspended in 10 ml of acetone and heated under reflux for 6 hours. The reaction solution was cooled to room temperature, toluene was added, insolubles were removed by filtration, and the filtrate was evaporated under reduced pressure. The obtained residue is subjected to silica gel column chromatography (toluene: ethyl acetate =
3: 1) to give the desired product (0.36 g)
I got

(2) 1- [O-sec-butyl- (2,
4,6-trimethyl) benzhydroxymoyl] -1H
Synthesis of 1-[(2,4,6-trimethyl) benzhydroxymoyl] triazole (0.51 g), potassium carbonate (0.4 g) and 2-iodobutane (0.55 g) in 20 ml of acetone And stirred at room temperature for 5 hours. The reaction solution was filtered, and the filtrate was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (toluene: ethyl acetate = 9: 1) to give the desired product (0.20).
g) was obtained.

(3) 1- [O-i-propyl- (2,
4,6-trimethyl) benzhydroxymoyl] -1H
-Synthesis of imidazole (compound 9) 1-[(2,4,6-trimethyl) benzhydroxymoyl] imidazole (0.61 g), potassium carbonate (0.48 g) and i-propyl iodide (2.92)
g) was suspended in 25 ml of acetone and heated under reflux for 4 hours. The reaction solution was filtered, and the filtrate was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (toluene: ethyl acetate = 9: 1) to obtain the desired product (0.17 g).

(4) 1- [O-i-propyl- (2,
4,6-trimethyl) benzhydroxymoyl] -1H
Synthesis of imidazole (compound 14) 1-[(2,4,6-trimethyl) benzhydroxymoyl] imidazole (0.45 g), potassium carbonate (0.4 g) and i-propyl iodide (0.4 g)
Was suspended in acetone (10 ml) and heated under reflux for 3 hours. The reaction solution was cooled to room temperature, toluene was added, insolubles were removed by filtration, and the filtrate was evaporated under reduced pressure. The obtained residue is subjected to silica gel column chromatography (toluene: ethyl acetate =
4: 1) to give the desired product (0.22 g)
I got

(5) Synthesis of other compound (1) in Table 1 Other compounds (1) in Table 1 were synthesized according to the methods described in the above (1) to (4). Table 1 shows the compound (1) synthesized as described above and the physical properties thereof.

[0033]

[Table 1]

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 sodium dodecylbenzenesulfonate and 2 parts by weight of sodium ligninsulfonate The parts were uniformly mixed, and then a small amount of water was added and kneaded, followed by extrusion granulation and drying to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 70 parts by weight of kaolin clay, 18 parts by weight of white carbon, 1.5 parts by weight of sodium dodecylbenzenesulfonate, and condensate of sodium formalin β-naphthalenesulfonate 0.5 parts by weight and uniformly mixed,
Subsequently, it was pulverized with an air mill 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 Solpol 3005X (trade name, manufactured by Toho Chemical) were added, mixed uniformly, 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 clay.

Example 3 [Biological test] (1) Paddy field weeding test A 1/5000 arel Wagner pot was filled with Ube soil (alluvial clay loam), and seedling rice, nobie, firefly, shrew beetle, konagi, and annual broadleaf ( Azena, Kikasigusa)
And tubers were planted, and water was added to a depth of 3 cm. The wettable powder of the target compound (1) shown in Table 1 prepared in accordance with Example 2 was diluted with water containing a surfactant (0.05%). The solution was dropped using a pipette so that the effective concentration of compound (1) in the solution was 2000 g / ha. And after controlling for 3 weeks in a glass room with an average temperature of 25 ° C., their herbicidal effect was investigated. The evaluation of the herbicidal effect was shown in the following six stages as compared with the state of the untreated section. 0: Normal growth, 1: Slight harm, 2: Small harm, 3: Medium harm, 4:
Major harm, 5: Complete withdrawal Note that "-" indicates that no examination has been made. Table 2 shows the results.

[0039]

[Table 2]

(2) Upland soil treatment test A 1/5000 arel Wagner pot was filled with Ube soil (alluvial clay loam), and seeds of Meechishiba, Nobie, Blackgrass, Shiroza, Inubiju and Japanese radish were planted and covered with soil. The wettable powder of the target compound (1) shown in Table 1 prepared according to Example 2 was diluted with water containing a surfactant (0.05%), and the compound (1) in each of these chemical solutions was diluted with water. Each soil surface was sprayed uniformly so that the effective concentration was 2000 g / ha. And 3 in a glass room with an average temperature of 25 ° C
After weekly management, their herbicidal effect was investigated. Evaluation of the herbicidal effect was performed in the same manner as in the above (1). In addition,
"-" Indicates that no study has been conducted. Table 3 shows the results.

[0041]

[Table 3]

(3) Upland field foliage treatment test 1/5000 arel Wagner pots were filled with volcanic ash soil, and seeds of Meechishiba, Nobie, Blackgrass, Shiroza, Inubeyu and Japanese radish were planted and covered with soil. Cultivated in the room for about 2 weeks. At the time when each plant had grown appropriately, a wettable powder of the target compound (1) shown in Table 1 prepared according to Example 2 was added to a surfactant (0.05
%) And diluted to 2,000 ppm with water, and sprayed uniformly on each of the above plants. After controlling for 3 weeks in a glass room at an average temperature of 25 ° C., their herbicidal effect was investigated.
Evaluation of the herbicidal effect was performed in the same manner as in the above (1). In addition,
"-" Indicates that no study has been conducted. Table 4 shows the results.

[0043]

[Table 4]

[0044]

The drug containing the benzhydroxymoylazole compound of the present invention as an active ingredient has an excellent herbicidal effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07D 403/12 C07D 403/12 (72) Inventor Tatsuo Okada 5-1978 Kogushi, Oji, Ube City, Yamaguchi Prefecture 5 Ube Industries Ube Research Laboratories F term (reference) 4C063 AA01 BB07 CC41 DD12 DD29 EE03 4H011 AB01 AB02 BA01 BB09 BC01 BC20 DA02 DA15 DA16 DD01 DD03 DD04 DE15

Claims (2)

[Claims] (1) The following formula (1): (Wherein R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms;
³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ⁴ is an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms having an alkoxycarbonyl group having 2 to 5 carbon atoms. Alkyl group, benzyl group, 2-5 carbon atoms
X represents an alkylcarbonyl group, a pyrimidyl group, a carbamoyl group having 2 to 5 carbon atoms, or a pyridyl group;
Represents CH and N. A herbicide characterized by comprising a benzhydroxymoylazole compound represented by the formula (1) as an active ingredient. 2. The method according to claim 1, wherein R ^{1 is}
And a benzhydroxymoylazole compound in which R ² is independently an alkyl group having 1 to 4 carbon atoms.