JPH04117309A - Herbicide composition for paddy field - Google Patents

Abstract

PURPOSE:To obtain the title composition controlling important weeds in paddy fields by one treatment, containing a 4-ethyl-3-substituted phenyl-(3-trifluoromethyl phenyl)-2-pyrrolidinone derivative and a sulfonylurea derivative as active ingredients. CONSTITUTION:The title composition containing a compound (new substance) shown by the formula (R is H, F or Cl; X is H, F, CF3, CH3, CN, NO2, etc.; n is 1 or 2) and 2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl-aminosulfonylmethyl] benzoic acid methyl ester, ethyl-5-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-1-methylpyrazo le-4-carboxylate, etc. The composition preferably contains 1 pt.wt. of the compound shown by formula I and 0.1-5 pts.wt. of each of the compounds, respectively and the composition can be used any period from prior to generation of weeds before rice transplanting to a growth period.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides novel 4-ethyl-3-(substituted phenyl)-1
The present invention relates to a herbicidal composition for paddy fields containing a -(3-trifluoromethylphenyl)-2-pyrrolidinone derivative and a sulfonylurea derivative as active ingredients.

[Prior Art] Conventionally, various compounds and mixtures have been known as herbicides for paddy fields. Furthermore, recently, a mixture of weeds that can control various weeds in a single treatment called one-shot treatment has been developed. However, these herbicides often require relatively large amounts of active ingredients, or are often unable to adequately control important weeds in a single treatment. It is desired to develop a herbicide for rice fields that can accurately control weeds.

[Problems to be Solved by the Invention] The present invention can be used at any time from before the emergence of weeds before rice planting to the growing season with a smaller amount of active ingredients, and can eliminate important weeds in rice fields with -1 treatment. The objective is to provide a herbicide for paddy fields that can control herbicides.

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted intensive research on mixtures of pyrrolidinone derivatives, and found that by mixing pyrrolidinone derivatives and sulfonylurea derivatives, the effects of each agent alone could not be expected. It shows a synergistic effect that cannot be achieved,
We have discovered that it is possible to obtain a herbicide for paddy fields that can be used at any time from before weeds emerge before rice planting to the growing season, and can control important weeds in paddy fields, by using a smaller amount of active ingredients.
The invention has been completed.

That is, the present invention relates to the general formula (1) (wherein R represents a hydrogen atom, a fluorine atom, or a chlorine atom, and X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom,
Represents a trifluoromethyl group, methyl group, cyano group or nitro group, n is 1 or 2 and represents the number of substituents represented by X, even if X in n = 2 is the same,
4-ethyl-3-(substituted phenyl)-1-( which may be different)
At least 1 M of a 3-trifluoromethylphenyl)-2-pyrrolidinone derivative and 2-((4,6-cymethoxypyrimidin-2-yl)aminocarbonyl-aminosulfonylmethyl)benzoic acid methyl ester (hereinafter referred to as compound A). ), ethyl-5-[3-(46-cymethoxypyrimidin-2-yl)-ureidosulfonyl-1-methylpyrazole-4-carboxylate (hereinafter referred to as compound B), 3-(4,6- Cymethoxy 1
,3.5-)riazin-2-yl)-1-(2-(
2-methoxyethoxy)-phenylsulfonyltourea (hereinafter referred to as compound C) or 1-(2-chloroimidazo(1,2-a)pyridin-3-ylsulfonyl)-3-(4,6-simethoxy2- pyrimidinyl)
- A herbicide composition for paddy fields, characterized by containing at least one kind of urea (hereinafter referred to as a compound) as an active ingredient.

Among the compounds contained in the composition of the present invention, general formula (I)
The compound group represented by is a new compound and can be produced by the following method.

That is, it can be easily produced by subjecting an amide derivative represented by general formula (II) to a reductive cyclization reaction.

(II) (In the above reaction formula, R, X, and n have the same meanings as above,
Y represents a halogen atom. ) Effective cyclizing agents for this cyclization reaction include trialkyltin hydrides such as tributyltin hydride. The reaction temperature to be carried out is 50~
140″C is preferable, more preferably 60-90′C
The reaction proceeds by adding a catalytic amount of a radical generating side such as α,α-azobisisobutyronitrile or benzoyl peroxide to the reaction mixture. Irradiation with light is also an effective means.

The amide derivative represented by the general formula (II) has the general formula (
It can be produced by reacting the amine of III) with the carboxylic acid derivative of general formula (IV).

(In the above formula, R, X, n, and Y have the same meanings as above, and Z represents a halogen atom.) The reaction is carried out without a solvent or in an inert solvent, and examples of the inert solvent include benzene, Aromatics such as toluene, xylene, chlorobenzene, dichloromenzene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethers such as diethyl ether, tetrahydrofuran, dioxane, esters such as ethyl acetate, butyl acetate, etc. can be given. In addition, aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide are also effective. The reaction proceeds at any temperature, and can be carried out in the presence of a base such as triethylamine, lysine, N,N dimethylaniline, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate. Good too.

Amines of formula (nI) are described in U.S. Pat.
It can be manufactured by the method described in . Also, the general formula (■
) can be produced from a manzolin acid derivative or a phenylacetic acid derivative by a known method.

Furthermore, the 4-ethyl-3-(2mphenyl)-1-(3)lifluoromethylphenyl)-2-pyrrolidinone derivative according to the present invention can be used to reduce the 2-pyrrolidinone derivative represented by the general formula (V). It can also be produced by dehalogenation.

(In the above reaction formula, R, X, Y, and n have the same meanings as above.) This reaction is carried out without a solvent or in a solvent in the presence of a suitable reducing agent. Examples of reducing agents include metals such as iron, zinc, tin, and copper, dialkyltin hydrides such as dibutyltin hydride, trialkyltin hydrides such as tributyltin hydride, diphenyltin hydride, and triphenyltin hydride. Examples include organic tin compounds. It is also possible to carry out the reaction using hydrogen in the presence of palladium carbon, Raney nickel, platinum, etc. In some cases, methods such as electrolytic reduction are also effective. Suitable solvents include aromatics such as benzene, toluene and xylene, ethers such as dioxane, tetrahydrofuran and styrene ether, esters such as ethyl acetate and butyl acetate,
Examples include lower alcohols such as methanol, ethanol, propatool, and butanol, and lower organic acids such as acetic acid, propionic acid, and butyric acid.The reaction temperature is 0 to 16.
0''C, and the reaction time may be from several seconds to 50 hours, and the reaction may be carried out at the reflux temperature of the solvent. It is also possible to carry out the reaction in the presence of acids.

The 2-pyrrolidinone derivative represented by general formula (V) is
The amide derivative of general formula (n) can be produced by carrying out a cyclization reaction in the presence of a suitable catalyst.

(II) (In the above reaction formula, R, Examples include dimethyl ether, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, benzene, toluene, and xylene. Suitable catalysts include transition metal catalysts, such as ferrous ions and cuprous ions. Specific examples of transition metal catalysts include ferrous chloride and cuprous chloride. It is also very effective to add amines to the reaction mixture in order to accelerate the reaction.The reaction temperature is 20-190°C, preferably 70-140°C.
It is C.

Compounds A, B, C, and D according to the present invention are all known compounds, and are disclosed in JP-A No. 57-112379 and
JP-A-59-122488, JP-A-57-564
No. 52, JP-A No. 1-139582, etc., and compound A is commercially available under the name bensulfuron methyl and compound B is commercially available under the name pyrazosulfuron ethyl. .

The compound represented by the general formula (+) has excellent activity as a herbicide for paddy fields, and is particularly active against barnyard grass, Japanese grasshopper, annual broadleaf, etc., but is less effective against perennial weeds such as weed grass. On the other hand, Compounds A, B, C, and D are known as herbicides that are highly effective against broad-leaved weeds such as Japanese grasshopper, but are less effective against barnyard grass.

In this way, the compound represented by the general formula (+) and compound A,
When B, C, and D are used alone, a sufficiently satisfactory herbicidal effect may not be expected in some cases.

Therefore, the present inventors prepared a compound of general formula (1) and a compound A.
When we investigated the mixed use of , B, C, and D, we found that they had a powerful synergistic effect that we could not have expected at first, and as a result, they could be used in far smaller quantities than when each was used alone, without causing any harm to paddy rice. We have discovered a herbicide composition that can accurately control important weeds.

The herbicidal composition according to the present invention thus obtained is generally mixed with an inert liquid carrier or solid and prepared into commonly used formulations such as powders, granules, wettable powders, emulsions, and flowables. used. Furthermore, if necessary for cleaving, an auxiliary agent can be added.

As the carrier, any solid or liquid carrier commonly used in agricultural and horticultural chemicals can be used, and the carrier is not limited to a specific one. For example, solid carriers include mineral powders such as clay, talc, bentonite, calcium carbonate, diatomaceous earth, and white carbon;
Examples include vegetable powders such as soybean flour and starch, polymeric compounds such as petroleum resins, polyvinyl alcohol, and polyalkylene glycols, urea, and waxes.

Examples of the liquid carrier include various organic solvents such as xolene, toluene, methylnaphthalene-1-alkylhenzene, and water.

As adjuvants, surfactants, binding agents, stabilizers, etc. commonly used in agricultural and horticultural chemicals can be used alone or in combination as required. Further, depending on the case, an industrial disinfectant or an antibacterial and antifungal agent may be added for antibacterial and antifungal properties.

As examples of surfactants, nonionic, anionic, cationic, and amphoteric surfactants can be used individually or in combination as appropriate. Preferred examples of nonionic materials include those obtained by adding ethylene oxide or propylene oxide to alkylphenols, higher alcohols, alkylnaphthols, higher fatty acids, fatty acid esters, and the like. As anionic substances, alkyl sulfonates, alkyl sulfate ester salts, phosphate ester salts, etc. of alkylphenols, alkylnaphthols, higher alcohols, higher fatty acids, fatty acid esters, etc. are preferable. Also preferred are lignin sulfonates and the like.

The general formula (1) which is a component of the herbicide composition according to the present invention
) and compounds A, B, C
, D can be expected to have an excellent herbicidal effect over a wide range of mixing ratios. However, the mixing ratio of the two is usually 0.00% each of Compounds A, B, C, and D to 1 part by weight of the pyrrolidinone derivative.
01 to 10 parts by weight, preferably 0.1 to 10 parts by weight of the compounds ThA, B, C, and D, respectively, per 1 part by weight of the pyrrolidinone derivative.
5 parts by weight.

The herbicide composition according to the present invention is effective in various treatment methods, but it is preferable to use it in waterlogged soil treatment.The mixture can be applied in a wide range of 0.05Kg to 50Kg/ha. It is possible, but the standard is 0.5Kg~5
It is preferable to use it in the range of Kg/ha.

The herbicide according to the present invention can be used in combination with one or more other herbicides, pesticides such as insecticides, fungicides, plant growth regulators, soil conditioners, or fertilizer substances. Of course, it is also possible to prepare a mixed preparation with these, and a synergistic effect can be expected in some cases.

[Example] The method for synthesizing the compound of the present invention will be explained by giving examples.

Example 1 4-ethyl-3-phenyl-1-(3-trifluoromethylphenyl)-2-pyrrolidinone (compound number 1.2
) Synthesis of N-(2-butenyl)-N-(3-
1.5 g of trifluoromethylphenyl)-2-chloro-2-phenylacetamide was added, and while stirring at reflux temperature, 1.2 g of tributyltin hydride and α,α-abbisisobutyronitrile (AIBN) electrode were added. Added a small amount.

After continuing stirring for 70 minutes, 40 d of saturated brine was added and extracted with toluene. After drying with anhydrous magnesium sulfate, concentrating with an evaporator and performing silica gel column chromatography, 3.4-) lance isomer 0.67
g and 0.27 g of 3,4-cis isomer were obtained.

Example 2 4-ethyl-3-(4-fluorophenyl)-1-(3
-trifluoromethylphenyl)-2-pyrrolidinone (
Synthesis of Compound No. 3.4) In 20d of toluene, N-(2-butenyl)-)l-(3
-trifluoromethylphenyl)-2-bromo-2-(
Add 1.9 g of 4-fluorophenyl)acetamide,
While stirring at 0 °C, add tributyltin hydride 1.2
d and α, α-azobisisobutyronitrile (AIB
N) A very small amount was added. After continuing stirring for 1 hour, 20% hydrochloric acid 60% was added and extracted with toluene. After drying over anhydrous sodium sulfate, the mixture was concentrated using an evaporator and subjected to silica gel chromatography to obtain 0.9 g of 3.4-) lance isomer and 0.27 g of 3.4-cis isomer.

According to the methods of Examples 1 and 2, the general formula (
Other pyrrolidinone derivatives represented by r) were synthesized.

Compounds represented by general formula (1) and their physical properties according to the present invention are listed in Table 1.

[Formulation Example and Test Example 1 Next, a formulation example of the herbicide according to the present invention and a herbicidal activity test example will be shown.

Formulation example 1 (hydrating powder) Compound (1): IQ parts by weight, Compound (A): 5 parts by weight,
Neoperex (trade name, manufactured by Kao; sodium dodecylhenzenesulfonate): 2 parts by weight, Neugen EA (trade name, manufactured by Dai-Kogyo Seiyaku; polyoxyethylene nonylphenyl ether) 22 parts by weight, White carbon: 5 parts by weight and ±76 parts by weight of diatoms were thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 (Powder) Compound (3): 1 part by weight, Compound (B): 0.2 part by weight, Emulgen 910 (trade name, manufactured by Kao; polyoxyethylene nonylphenyl ether): 0.5 part by weight, and Kaolin clay: 98.3 parts by weight was thoroughly ground and mixed to obtain a powder.

Formulation Example 3 (Granules) Finely ground compound (5): 0.2 parts by weight, finely ground compound (C): o, 2 parts by weight, Neoperex (trade name,
After thoroughly mixing 22 parts by weight of Sunextract P252 (trade name, manufactured by Sanyo Kokusaku Valve; sodium lignin sulfonate), 70.6 parts by weight of bentonite and 25 parts by weight of talc, of water was added to moisten it and then extruded and granulated in a small injection molding machine. After air-drying and crushing this at 30-60°C, it was granulated to 0.3-2I using a granulator to obtain granules.

Formulation Example 4 (Flowable agent) Compound (25): 3 parts by weight, Compound (A):
parts by weight of x, s and 10 parts by weight of Sunextract P252 (trade name, same as above) dissolved in 60.5 parts by weight of water were wet-pulverized and mixed, and Kelsan S was dissolved in 24.6 parts by weight of the condensed water. (Product name, made by Kelco; .

Test Example 1 Soil mixing treatment before rice planting (pre-emergence treatment) 1150
Fill soil in 00 Earl Wagner pot, and grow Tainubier.
Seeds or tubers of Konagi, Firefly, and Urikawa were sown and flooded. A predetermined amount of the test composition was treated with a flowable agent prepared according to the method described in Formulation Example 4, and the agent was mixed to a soil width of about 2 CII. After 4 days, two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were added to 1
The two plants were transplanted and grown in a greenhouse. 3
After 0 days, the growth status of weeds and the status of chemical damage to paddy rice were investigated. The results are shown in Table 2.

In the table, the degree of damage to the test plants and the degree of phytotoxicity to paddy rice are expressed by comparing the growth state of the plants with those without treatment and using the following criteria.

5 0-5 4 6-10 3 11-40 2 41-70 1 71-90 0 91-100 (Death) Pre-emergence treatment) 11500
A Wagner pot was filled with soil, and seeds or tubers of Japanese cabbage, Japanese cabbage, firefly, and Urikawa were sown, and the pots were flooded with water. Paddy rice seedlings (2
~3-leaf stage) Two plants were taken as one plant, and the two plants were transplanted and grown in a greenhouse. Three days later, a predetermined amount of the test composition was treated with granules prepared according to the method described in Formulation Example 3, and the growth status of weeds and the status of chemical damage to paddy rice after 30 days were investigated. The results are shown in Table 3.

In the table, the degree of damage to the test plants and the degree of chemical damage to paddy rice are shown in the same manner as in Test Example 1.

As shown in Table 2.3 above, the herbicide composition according to the present invention can accurately control most important weeds in paddy fields without causing any harm to paddy rice.

Furthermore, their herbicidal effects exhibit superior synergistic action compared to each agent alone, making it possible to expand the herbicidal spectrum and use lower doses.

[Effects of the Invention] The herbicidal composition according to the present invention has a herbicidal effect that can be expected when the pyrrolidinone derivative represented by the general formula (1) and each of Compounds A, B, C, and D are used alone. Due to its extremely high synergism, it is effective against most important weeds in rice fields at lower dosages. As a result, the herbicide composition according to the present invention can accurately control important weeds in paddy fields with a single treatment, and has high applicability as a herbicide for paddy fields, and the present invention provides an extremely useful herbicide. It is.

Claims (1)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a hydrogen atom, a fluorine atom, or a chlorine atom, and X represents a hydrogen atom, a fluorine atom, a chlorine atom, or a bromine atom. atom,
Represents a trifluoromethyl group, methyl group, cyano group or nitro group, n is 1 or 2 and represents the number of substituents represented by X, even if X in n = 2 is the same,
May be different. ) 4-ethyl-3-(substituted phenyl)-1-(
At least one kind of 3-trifluoromethylphenyl)-2-pyrrolidinone derivative, and 2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl-aminosulfonylmethyl]benzoic acid methyl ester, ethyl-5- [3-(4,6-dimethoxypyrimidin-2-yl)-ureidosulfonyl]-1-methylpyrazole-
4-carboxylate, 3-(4,6-dimethoxy-1
,3,5-triazin-2-yl)-1-[2-(2-
methoxyethoxy)-phenylsulfonyl]-urea or 1-(2-chloroimidazo[1,2-a]pyridin-3-ylsulfonyl)-3-(4,6-dimethoxy-
1. A herbicidal composition for rice fields, comprising at least one sulfonylurea derivative consisting of 2-pyrimidinyl)-urea as an active ingredient.