WO2001016112A1

WO2001016112A1 - Benzoate compounds, herbicides and method of using the same

Info

Publication number: WO2001016112A1
Application number: PCT/JP2000/005720
Authority: WO
Inventors: Yuzo Miura; Tsutomu Mabuchi; Takashi Ohtsuka
Original assignee: Nihon Nohyaku Co., Ltd.
Priority date: 1999-08-26
Filing date: 2000-08-24
Publication date: 2001-03-08
Also published as: AU6729300A

Abstract

Benzoate compounds represented by general formula (I) and herbicides containing these compounds as the active ingredient, wherein R represents isopropyl, -CH2COOR1 (wherein R1 represents C¿1-3? alkyl) or -CH(CH3)COOR?1¿ (wherein R1 is as defined above) when Y is bromo, or R represents isopropyl when Y is chloro. The herbicides containing the benzoate compounds represented by general formula (I) have an excellent herbicidal activity in a small dose in soil treatment and a high selectivity among crops and weeds, which makes them highly useful in elevating agricultural productivity.

Description

Specification

Benzoic acid ester compound, herbicide and method of using the same

Technical field

The present invention relates to a benzoate ester compound represented by the general formula (I), a herbicide containing the compound as an effective component, and a method for using the same.

Background art

Japanese Patent Application Laid-Open No. 3-163603 describes that a 3-substituted pentavirazole derivative containing the compound of the present invention in the general formula is useful as a herbicide. However, there is no description at all of the benzoic acid ester compound represented by the general formula (I) of the present invention, such as physical properties and methods of use.

At present, there is a strong demand for the creation of herbicides that are active at low doses and have high selection between crops and weeds.Efficient weed control requires not only foliar treatment herbicides but also soil Processed herbicides are also needed. Agricultural work requires various types of work, but weeding is an important and labor-intensive task. If weeding work can be done at the same time as other work or at a time when it does not conflict with other work, it will lead to more efficient agricultural production. In recent years, with the development of agricultural machinery, machines that can carry out various types of work in parallel have emerged. Machines that can spray fertilizers and pesticides simultaneously with rice planting are known. Spraying the herbicide along with cultivation is efficient because subsequent weeding work can be omitted.

The present inventors have conducted intensive studies to develop a herbicide having a high activity at a low dose and a high selectivity in soil treatment. As a result, the benzoate ester compound represented by the general formula (I) of the present invention was obtained. Is a novel compound not described in the literature, exhibits excellent herbicidal activity as compared with the compound disclosed in JP-A-3-16363, and has high selectivity in soil treatment. The present invention has been completed.

Disclosure of the invention

The present invention provides a compound of the general formula (I):

(In the formula, when Y is a bromine atom, R is an isopropyl group, and CHsCOOR ¹ (in the formula, denotes a ^ alkyl group.) Or — CH (CH ₃ ) COOR ¹ (where R ¹ is Same as above.)), And when Y is a chlorine atom, R represents an isopropyl group.)

And a herbicide containing the compound as an active ingredient and a method of using the same. '

In the definition of the general formula (I) of the present invention, “C i -C ₃ alkyl group” means a linear or branched alkyl group having 1 to 3 carbon atoms, for example, a methyl group, an ethyl group , A normal propyl group and an isopropyl group.

The preferred compounds of the present invention include, for example, 2-chloro-5- (4-chloro-5-difluoromethoxy-1--1-methyl-1H-pyrazolone-3-yl) -4-isopropynole 4-benzoylbenzoate, —Chloro-1- (4-bromo-5-difluoromethoxy) -1-methyl-1H-pyrazole-13-yl) —Isopropyl-4-fluorobenzoate.

BEST MODE FOR CARRYING OUT THE INVENTION

The compound of the present invention can be produced according to the method described in JP-A-3-163063. For example, it can also be produced by the production method shown below.

(In the formula, R and Y are as defined above, and Ζ represents a halogen atom.)

The compound represented by the general formula (1-3) is subjected to a halogenation reaction with a halogenating agent in the presence or absence of an inert solvent to obtain an acid halide represented by the general formula (1-2). The acid halide is isolated or not isolated and reacted with an alcohol represented by the general formula (II), or the compound represented by the general formula (1-3) is reacted in the presence of an inert solvent. Or reacting with an alcohol represented by the general formula (III) in the presence or absence of a mineral acid, or a compound represented by the general formula (1-3) in the presence or absence of an inert solvent By reacting with a halide represented by the general formula (III) in the presence of a dehalogenating agent, it is possible to produce the desired benzoate compound represented by the general formula (I). it can.

(1). General formula (1-3) → General formula (1-2).

This reaction is an acid halide reaction. Examples of inert solvents that can be used in this reaction include halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, and aromatic solvents such as benzene, toluene, and xylene. Acyclic or cyclic ethers such as aromatic hydrocarbons, methyl sorb, methyl ether, diisopropyl ether, dioxane, and tetrahydrofuran can be used, and these inert solvents are used alone or in combination. You can also.

As the halogenating agent, for example, thionyl chloride, phosphorus pentachloride, phosphorus trichloride and the like can be used. The amount of the halogenating agent used is based on the compound represented by the general formula (I-3). The amount may be appropriately selected from the range of equimolar to excess mole, and preferably used in excess. The reaction can also be performed by adding a catalytic amount of triethylamine, pyridine, dimethylformamide, tetramethylthiourea or the like for the purpose of accelerating the reaction.

The reaction temperature may be selected from the range of room temperature to the boiling point of the inert solvent to be used. The reaction time is not fixed depending on the reaction amount and the reaction temperature, but may be appropriately selected from the range of several minutes to 48 hours.

After completion of the reaction, the target compound may be isolated by removing the excess halogenating agent and solvent from the reaction solution containing the target compound by distillation or the like, and the target compound may be isolated by a method such as a recrystallization method or a distillation method, if necessary. It can be used for the next reaction after purification, or can be used for the next reaction without isolation and purification.

(2). General formula (1-2) or General formula (1-3) — General formula (I)

In this reaction, in the esterification reaction, the alcohol represented by the general formula (II) is used in excess in the presence of a mineral acid, for example, concentrated sulfuric acid, and can be used as a reactant and a solvent. Further, the compound of the general formula (1-3) can be used in the form of a salt such as an alkali metal atom. Further, the esterification reaction can be carried out in the presence of an inert solvent and a depilation agent. In this case, examples of the inert solvent that can be used include those of the inert solvent used in the acid halide reaction. In addition, non-protonic solvents such as ketones such as acetone, dimethylformamide, dimethylsulfoxide, dimethylimidazole, and dimethylacetamide can be used.

The amount of the alcohol represented by the general formula (II) or the halide represented by the general formula (II) may be appropriately selected and used from the range of equimolar to excess molar, and is preferably used in excess molar. Good to do.

As the dehalogenating agent that can be used in this reaction, an inorganic base or an organic base can be used. For example, a hydroxide of an alkali metal atom such as sodium hydroxide or potassium hydroxide, and an organic base such as triethylamine And organic bases such as 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] —7-pinedecene, etc., and the amount used is The acid halide represented by the general formula (1-2) is appropriately selected and used in the range of equimolar to excess molar. Just do it.

The reaction temperature may be selected from the range of o ° C to the boiling point of the solvent used, preferably from 0 ° C to 150 ° C.

The reaction time is not fixed depending on the reaction amount, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours.

After completion of the reaction, the reaction solution is subjected to an operation such as solvent extraction by a conventional method and, if necessary, purified by a method such as a recrystallization method, a distillation method, or a column chromatography method to obtain a compound represented by the general formula (I) ) Can be produced.

Table 1 shows typical benzoate compounds represented by the general formula (I).

General formula (I):

Table 1

No Y R Physical properties (refractive index)

1 CI-i-C ₃ H ₇ nD 1.5273 (24.3.C)

_{_{2 Br - i- C 3 H 7}} nD 1.5403 (28.7 .C)

_{_{3 Br - CH 2 C00CH 3 nD}} 1.5465 (26.2 .C)

4 Br -CH ₂ C00C ₂ H ₅ nD 1.5420 (26.3.C)

_{5 Br -CH (CH 3) C00CH} 3 nD 1.5398 (26.9 .C)

_{6 Br -CH (CH 3) C00C} 2 H 5 nD 1.5343 (28.7 .C) Herbicides containing the benzoate ester compound represented by the general formula (I) of the present invention as an active ingredient include, for example, barnyardgrass (Poaceae, first grade, paddy field weeds), tamagayari (Ricaridasa family, annual grass, paddy field) Pests), pine trees (perennial grasses of the scrophulariaceae, wetlands, waterways, and paddy fields, perennial grasses of paddy fields), ゥ rika ヮ (perennial grasses of the ophidaceae, paddy fields, wetlands, ditches), fireflies Perennial grasses, perennial grasses, rice fields, wetlands, ditches, sparrows (grass weeds, rice fields, lowlands), Empak (grass annuals, flatlands, wastelands, fields), sagebrush (kiku) Perennial grass, occurring in the mountains and fields, grasshoppers (first-year grasses, fields, and orchards), rubbing (perennials, perennials, fields, and roadsides), kogomajarari Grass family 1st year grass, Aobu (Hygaceae 1st year grass, vacant lot, roadside, upland), bonafami (Asteraceae 1st year grass, upland grass), Ichibi (1st year grass, upland grass) Grass), Ipomoea japonicus (Goldenaceae, 1st year grass, field grass), Ooinoufuguri (1st to 2th year grass, field grass), Yaemdara (1st year grass, grassland, orchard) It is useful for weeding annual and perennial weeds that occur in paddy fields, fields, orchards, wetlands, etc.

The herbicide containing the benzoic acid ester compound represented by the general formula (I) of the present invention as an active ingredient has an excellent herbicidal effect on weeds before and after budding, particularly, an excellent herbicidal effect by treatment before budding. Is shown. The mode of application is that if pre-treated at the site where the useful plants are to be planted, power is applied \ after sowing and planting of the useful plants (including when the useful plants have already been planted like an orchard) Before the emergence of weeds By treating at an early stage, the characteristic physiological activity of the herbicide of the present invention can be effectively expressed.

However, the herbicide of the present invention must be used only in such an embodiment. However, for example, the herbicide of the present invention can be used as a herbicide for paddy fields, and a herbicide for general weeds. For example, mowing marks, fallow fields, levees, agricultural roads, waterways, pastures, cemeteries, parks, roads, playgrounds, vacant lots around buildings, reclaimed land, track ends, forests, etc. It can also be used to control weeds. In this case, it is most economically effective to treat weeds until the beginning of their emergence, but it is not necessarily limited to this, and weeds in the growing season can be controlled. Preferably, it is used before the occurrence of weeds. When the benzoate compound represented by the general formula (I) of the present invention is used as an active ingredient as a herbicide, the benzoate compound is formulated into a convenient form in accordance with a conventional method for agricultural chemicals. Is common.

That is, the benzoate compound represented by the general formula (I) is dissolved, separated, suspended by mixing these in an appropriate inactive carrier or, if necessary, together with an auxiliary in an appropriate ratio. It may be mixed, impregnated, adsorbed or adhered and formulated into an appropriate dosage form, such as a suspension, emulsion, liquid, wettable powder, granule, powder, tablet or the like.

The inert carrier that can be used in the present invention may be either solid or liquid. Examples of the material that can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, saw flour, and tobacco stem flour. , Walnut shell powder, bran, cellulose powder, residue after extracting plant extracts, synthetic polymers such as pulverized synthetic resin, clays (for example, kaolin, bentonite, acid clay), tanoleks (for example, talc, pyrophyllide) ), Silica (for example, diatomaceous earth, silica sand, mica, and white carbon [Synthetic high-dispersion silicic acid also known as hydrous finely divided silicon and hydrous silicic acid, some of which contain calcium silicate as a main component depending on the product.)], Activated carbon, zeolite Powder, pumice, calcined diatomaceous earth, crushed brick, fly ash, sand, inorganic mineral powder such as calcium carbonate, calcium phosphate, and ammonium sulfate Phosphate weaker ammonium nitrate, can be mentioned urea, fertilizer salts depreciation etc., compost and the like, which may be used alone or as a mixture of two or more.

As a material that can be a liquid carrier, other than a material having a solvent function itself, any material that does not have a solvent function and can disperse the compound of the present invention with the aid of an auxiliary agent may be used. Alcohols (eg, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones (eg, acetone, methylethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (eg, Ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, kerosene, mineral oil, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, alkyl naphthalene, etc.), halogen Hydrocarbons (Eg, dichloroethane, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), Examples include amides (eg, dimethylformamide, getylformamide, dimethylacetamide, etc.), nitriles (eg, acetonitrile, etc.), dimethylsulfoxides, and the like. These may be used alone or in combination of two or more. It can be used as a mixture.

Examples of other adjuvants include the following representative adjuvants.These adjuvants are used according to the purpose, and may be used alone or, in some cases, in combination of two or more adjuvants. However, in some cases, it is possible to use no adjuvant at all.

A surfactant is used for the purpose of emulsifying, dispersing, solubilizing and Z or wetting the compound of the present invention, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene. Surfactants such as resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylaryl sulfonate, naphthalene sulfonic acid condensate, lignin sulfonate, and higher alcohol sulfate ester Can be exemplified.

Further, for the purpose of dispersion stabilization, adhesion and / or binding of the compound of the present invention, for example, casein, gelatin, starch, methylsenorellose, carboxymethinolecellulose, gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite Auxiliaries such as lignin sulfonate can also be used.

For improving the fluidity of solid products, auxiliary agents such as wax, stearate and alkylester phosphate can be used.As peptizers for suspending products, for example, naphthalenesulfonic acid condensate, condensed phosphate, etc. Auxiliaries can also be used.

As an antifoaming agent, for example, an auxiliary agent such as silicone oil can be used. The compounding ratio of the compound of the present invention can be adjusted as required. For example, when it is used as a powder or granules, it is 0.01 to 50% by weight, and when it is used as an emulsion or a wettable powder. Same 0 :! ~ 50% by weight is suitable.

The herbicide containing the compound of the present invention as an active ingredient is effective for killing or suppressing growth of various kinds of weeds, either as it is, or appropriately diluted with water or the like, or suspended to form a suspension. A large amount can be applied to the weed or to the foliage or soil in places where the occurrence or growth of the weed is not preferred. The amount of the herbicide containing the compound of the present invention may vary depending on various factors, for example, the purpose, the target weed, the growth status of the crop, the tendency of weed occurrence, the weather, the environmental conditions, the dosage form, the method of application, the place of application, and the time of application. Although it fluctuates, it is advisable to appropriately select the active ingredient compound from the range of 0.1 g to 10 kg per hectare according to the purpose.

The herbicide containing the compound of the present invention can be used in admixture with other herbicides for controlling weeds to be controlled, extending the suitable period of control, or reducing the dose.

The herbicide containing the benzoate ester compound represented by the general formula (I) of the present invention has excellent herbicidal activity at a low dose in soil treatment, and has high selectivity between crops and weeds. It is useful for improving agricultural productivity.

Example

Hereinafter, typical examples, preparation examples, and test examples of the present invention are shown, but the present invention is not limited thereto. In the preparation examples, “parts” means “parts by weight”.

Example 1. 2-chloro-1-5- (4-chloro-5-diphnoleolomethoxy-1-methyl-1H-pyrazol-3-yl) isopropyl-14-fluorobenzoate (diamide compound No. 1) Manufacturing of

2-chloro-5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole-3-yl) -4-fluorobenzoic acid 1.705 g (0.0047 7 mol), dimethylsulfoxide 40m and anhydrous potassium carbonate A mixture of 0.989 g (0.00716 mol) and 1.218 g (0.0071 6 mol) of isopropyl iodide was reacted at room temperature for 4 hours. After completion of the reaction, the reaction mixture was poured into 200 ml of ice water, the desired product was extracted with ethyl acetate, the organic layer was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The target product was converted to an oily substance by purifying the obtained residue by HPLC. 858 g were obtained.

Physical properties: nD l. 5273 (24.3 ° C)

Yield: 97.8%

Example 2. 2-chloro-1-5- (4-bromo-5-difluoromethoxy-1-methyl-1H-pyrazole-3-yl) -14-isopropyl-4-benzoate isopropyl ) Manufacturing of

2- chloro 5- (4- bromo-5-Jifunoreo port main butoxy one 1 Mechinore one 1 H - Birazo - Le _ _three to I le) one 4 _ Furuoro benzoate 0. i 5 g (0. 00037 mol), dimethyl A mixed solution of 20 ml of sulfoxide, 0.077 g (0.00056 mol) of anhydrous potassium carbonate and 0.095 g (0.00056 mol) of isopropynole iodide was reacted at room temperature for 4 hours. After completion of the reaction, the reaction mixture was poured into ice water (8 Om1), the desired product was extracted with ethyl acetate, the organic layer was washed with water, washed with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was depressurized. The residue was purified by silica gel gel chromatography to obtain 0.12 g of the desired product as an oil.

Physical properties: nD l. 5403 (28.7 ° C)

Yield: 72.4%

Formulation example 1.

Compounds listed in Table 1 50 parts

Xylene 40 parts

Polyoxyethylene nonylphenyl ether

Mixture with calcium alkylbenzenesulfonate 10 parts

The above are uniformly mixed and dissolved to form an emulsion.

Formulation example 2. Compounds listed in Table 1 3 parts

Cray powder 8 2 parts

Diatomaceous earth powder 1 5 parts

The above is uniformly mixed and pulverized into a powder ₍

Formulation example 3.

Compounds listed in Table 1 5 parts

90 parts mixed powder of bentonite and clay

Lignin sulfonic acid canolesum 5 parts

The above components are mixed uniformly, kneaded by adding an appropriate amount of water, granulated and dried to obtain granules. Formulation example 4.

Compounds listed in Table 1 20 parts

Kaolin and synthetic high dispersion silicic acid 75 parts

Polyoxyethylene Noninolefenenolate and Anole

5 parts of a mixture with kilbenzenesnolephonate canolesum

The above is uniformly mixed and ground to form a wettable powder.

Test Example 1. Herbicidal effect on field weeds before emergence

The soil was packed in a plastic vat measuring 10 cm in length, 20 cm in width, and 5 cm in height, and seeds were covered with soybean chamomile, Hakobe, violet and wheat (variety: Anza, Anza). To this, a drug having a compound shown in Table 1 or a comparative compound as an active ingredient was applied as a spray solution having a predetermined concentration. The herbicidal effect was investigated 28 days after the treatment. The judgment value by the naked eye judgment [0 (no activity or no phytotoxicity) to 100 (complete withering)] was recorded. The phytotoxicity to wheat was investigated 7 days after treatment and 28 days after treatment, and the judgment value by the visual judgment value was recorded.

In addition, if the damage is more than 20 with the naked eye judgment, it will affect the yield and is unacceptable for agricultural production. The results are shown in Table 1. Table 2

Comparative compound: Compound No. 498 described in JP-A-3-16363 was used.

[2-Chloro-5- (4-chloro-5-difnoleolomethoxy-1 1-methyl-1H-pyrazole-3-yl) -methyl 4-fluorobenzoate]

Claims

The scope of the claims

1. General formula (I):

(In the formula, when Y is a bromine atom, R is an isopropyl group, and CHsCOOR ¹ (wherein R ¹ represents a C _C ₃ alkyl group.) Or — CH (CH ₃ ) COOR ¹ (wherein R ¹ Is the same as above.), And when Y is a chlorine atom, R represents an isopropyl group.)

A benzoic acid ester compound represented by the formula:

2. The benzoic acid ester compound is 2-chloro-5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole-13-yl) -isopropyl-4-fluorobenzoate, 2-chloro-5- (4-Bromo-5-diphnoleolomethoxy-1-methyl-1H-pyrazole-13-yl) 4-Fluorobenzoic acid isopropyl, 2-chloro-5- (4-Bromo-5-difluoromethoxy-1 —Methynolei 1 H—Pyrazole-13-yl) -14-Methoxycarbonylmethyl 4-fluorobenzoate, 2-chloro-5- (4-Bromo-5-difluoromethoxy-1 1-methyl-1 H-pyrazole-1 3 4-yl ethoxycarbonylmethyl benzoate, 4-chloro-5- (4-bromo-5-difluoromethoxy-1-methyl-1H-pyrazole-3-yl) 1-4-fluorobenzo Acid 1 i (main Tokishikarubo) yl Echinore or 2 black opening one 5- (4 _ bromo one 5- Jifunoreorome butoxy one 1 - methyl - 1 H- pyrazol - 3-I le) one 4 one Furuoro benzoate

The benzoate ester conjugate according to claim 1, which is 1- (ethoxycarbonyl) ethyl.

3. Contains the benzoate compound according to claim 1 or 2 as an active ingredient A herbicide characterized by that:

4. The herbicide according to claim 3, wherein the herbicide is a herbicide for soil treatment.

5. The herbicide for soil treatment according to claim 3, wherein the object to be treated is wheat.

6. A method for using a herbicide, which comprises applying an effective amount of the herbicide according to any one of claims 3 to 5 to a target plant or soil.