JPH04112802A - Herbicide composition for paddy field - Google Patents

Abstract

PURPOSE:To obtain a herbicide composition for paddy field capable of surely controlling principal weeds in the paddy field for a long period of time with a lower amount of agent and a time of treatment containing a new specific pyrrolidinone derivative and a specific chloroacetamide derivative as active ingredients. CONSTITUTION:The aimed herbicide composition for paddy field having above- mentioned effect contains (A) a new substance expressed by formula I (R is H, F or Cl; X is H, F, Cl, Br, CF3, CH3, CN or NO2; n is 1 or 2 and X may be different for n=2) and (B) at least a species of 2-chloro-2'.6'-diethyl- N-(butoxymethyl)-acetanilide, 2-chloro-2'.6'-diethyl-N-(n-propoxyethyl)-acetanilide or 2-chloro-2'.6'-dimethyl-N-(3-methoxy-2-thienyl)methyl acetanilide as active ingredients. Besides, the new substance expressed by formula I is readily produced by reducing cyclization reaction of a compound expressed by formula II (Y is halogen).

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 rice fields containing a -(3-trifluoromethylphenyl)-2-pyrrolidinone derivative and a chloroacetamide derivative as active ingredients.

[Prior Art] Conventionally, various compounds and mixtures have been known as herbicides for paddy fields. Furthermore, recently, a mixture called a one-shot treatment agent that can control various weeds with a single treatment has been developed. However, these herbicides often require a relatively large amount of active ingredients, or even though they are called pesticides, cannot accurately control important weeds in a single treatment, or their effectiveness is short-lived. Therefore, with a smaller amount of active ingredients,
It is desired to develop a herbicide for rice fields that can accurately control important weeds and has a long-lasting effect.

[Problems to be Solved by the Invention] The present invention uses a smaller amount of active ingredients, can be used at any time from the time when weeds are ordered before rice planting to the growing season, 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 for a long period of time.

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted extensive research on mixtures of pyrrolidinone derivatives, and found that by mixing pyrrolidinone derivatives and acetamide derivatives, the effects of each of them alone can be improved. A herbicide for paddy fields that exhibits unexpected synergistic effects and can be used at any time from before weeds emerge before rice planting to the growing season, using fewer active ingredients, and can control important weeds in paddy fields over a long period of time. The present invention was completed based on the discovery that the following can be obtained.

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-( may be different)
3 trifluoromethylphenyl)-2-pyrrolidinone derivatives and 2-chloro-2,6''-
Diethyl-N-(butoxymethyl)-acetanilide (
(hereinafter referred to as compound @IJA), 2-chloro-2',6-diethyl-N-(n-propoxyethyl)-acetanilide (hereinafter referred to as compound B) or 2-chloro-26'-dimethyl-N-(3-methoxy -2-thienyl) methylacetanilide (hereinafter referred to as compound C) as an active ingredient.

Among the compounds contained in the composition of the present invention, -C formula (1)
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 the amide derivative represented by general formula (n) to a reductive cyclization reaction.

By adding it inside, the reaction will proceed. Irradiation with light is also an effective means.

The amide derivative represented by the general formula (I[) is the amide derivative represented by the general formula (I[).
It can be produced by reacting the amine of [[) with the carboxylic acid derivative of general formula (IV).

(n) (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 takes place in the solvent of the system. The reaction temperature is 50~
140'C is preferable, more preferably 60-90°C
Then, a catalytic amount of a radical generator such as α α-azobisisobutyronitrile or benzoyl peroxide was added to the reaction mixture (I[[) (in the above formula, R, X, n, and Y have the same meanings as above). , Z represents a halogen atom) The reaction is carried out without a solvent or in an inert solvent. Examples of inert solvents include aromatics such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene, dichloromethane, chloroform, Examples include halogenated hydrocarbons such as carbon tetrachloride, ethers such as diethyl ether, tetrahydrofuran, and dioxane, and esters such as ethyl acetate and butyl acetate. In addition, aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide are also effective. The reaction proceeds at any temperature, and may be carried out in the presence of a base such as triethylamine, pyridine, N,N-dimethylaniline, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate. Good too.

Amines of formula (If) are described in U.S. Pat.
Manufactured by the method described in, etc. 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-(substituted phenyl)-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.

(V) Y (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, triphenyltin hydride, etc. 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, dioxane,
Examples include ethers such as tetrahydrofuran and diethyl ether, esters such as ethyl acetate or butyl acetate, 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 0-1
60°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.

The 2-pyrrolidinone derivative represented by general formula (V) is
It is produced by subjecting the amide derivative of general formula (n) to a cyclization reaction in the presence of a suitable catalyst.

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

Compounds A, B, and C according to the present invention are all known compounds, and are disclosed in Japanese Patent Publication No. 53-35060, Japanese Patent Application Laid-Open No. 49-54527, and Japanese Patent Application Laid-open No. 60-4181, respectively. Furthermore, compound A is commercially available under the general name butachlor, and compound B is commercially available under the general name pretirakushiru, and is in practical use.

The compound represented by the general formula (1) has excellent activity as a herbicide for paddy fields, and has high activity in pre-emergence treatment, especially for barnyard grass, grasshopper, annual broadleaf, etc., and has a long-lasting effect.
However, its effectiveness against perennial weeds such as firefly is somewhat low, and its effectiveness during the growing season is generally poor. - Compounds A, B, and C are effective against many weeds such as barnyard grass, grasshopper, and bulrush from the pre-emergence period to the growing season, but when used in low dosages, the effect is large and the duration of the effect is short. It's also short.

In this way, the compound represented by general formula (I) and compound A,
B and C, when used alone, are not fully satisfactory in terms of timing of use and duration of effect.

Therefore, the present inventors prepared a compound of general formula (1) and a compound A.
When we investigated the mixed use of , B, and C, we found that they had a powerful synergistic effect that we could not have expected at first, and as a result, using a much smaller amount than when using each of them alone, weeds can be used from before weeds appear before rice planting to during the growing season. We have discovered a herbicide composition that can control important weeds in paddy fields for a long period of time without causing any harm to rice fields.

The herbicidal composition according to the present invention thus obtained is generally mixed with an inert liquid carrier or a solid, and applied to commonly used formulations such as powders, granules, wettable powders, porous preparations, flowable preparations, etc. Adjusted and used. Furthermore, if necessary for the formulation, auxiliary agents 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 xylene, toluene, methylnaphthalene, and alkylhenzene, and water.

As adjuvants, surfactants, binders, 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 the compound I! l1lI
Excellent herbicidal effects can be expected in a wide range of mixing ratios with A, B, and C. However, the mixing ratio of the two is usually 1 part by weight of the pyrrolidinone derivative to 1 part by weight of the compound A, B, CO,
~100 parts by weight, preferably 1 to 20 parts by weight of compounds A, B, and C per 1 part by weight of the pyrrolidinone derivative.

The herbicide composition according to the present invention is effective in various treatment methods, but it is preferably used in hot water soil treatment, and the mixture can be used in a wide range of application amount from 0.01 Kg to 10 Kg/ha. However, the standard is 0.1kg~I
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, insecticides, fungicides, pesticides such as plant growth moderators, soil conditioners, or fertilizer substances. Of course, it is also possible to prepare a mixed preparation with these, and in some cases, a synergistic effect can be expected.

[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-trifluoromethylphenyl)-2-chloro-2-
1.5 g of phenylacetamide was added, and while stirring at reflux temperature, 1.2 g of tributyltin hydride and a very small amount of α,α-azobisisobutyronitrile (AIBN) were added. After continued 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
~Synthesis of trifluoromethylphenyl)-2-pyrrolidinone (compound number 3.4) In 20d of toluene, N-(2-butenyl)-N-(3-
) fluoromethylphenyl)-2-furomo2-(4
-Add 1.9 g of fluorophenyl)acetamide, and
While stirring at <0>C, 1.2 mm of tributyltin hydride and a trace amount of α,α-azobisisobutyronitrile (AIBN) were added. After stirring for 1 hour, 20% hydrochloric acid 60
d was added and extracted with toluene. After drying with anhydrous sodium sulfate, concentrating with an evaporator and performing silica gel chromatography, 3.4-) lance isomer 0
．． According to the methods of Examples 1 and 2 in which 9 g and 0.27 g of the 3.4-cis isomer were obtained, other pyrrolidinone derivatives represented by the general formula (1) according to the present invention were synthesized.

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

[Formulation Examples and Test Examples] Next, formulation examples and herbicidal activity test examples of the herbicide according to the present invention will be shown.

Formulation example 1 (hydrating powder) Compound (1): 10 parts by weight, Compound (A): 2Q parts by weight, Neoperex (trade name, manufactured by Kao; sodium dodecylbenzenesulfonate): 2 parts by weight, Neugen EA (trade name) 2 parts by weight of polyoxyethylene nonylphenyl ether (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 5 parts by weight of white carbon, and ±61 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): 2 parts by weight, Emulgen 910 (trade name, manufactured by Kao; polyoxyethylene nonylphenyl ether): o, s parts by weight, and kaolin clay. : 96.5 parts by weight were thoroughly ground and mixed to obtain a powder.

Formulation Example 3 (Granules) Finely pulverized compound (5): 0.2 parts by weight, finely pulverized compound (C): 1 part by weight, Neoperex (trade name, same as above): 2 parts by weight, Sunextract P252 (trade name, manufactured by Sanyo Kokusaku Pulp; sodium lignin sulfonate) = 2
Parts by weight, hentonite = 71.8 parts by weight and talc:
After 23 parts by weight were thoroughly mixed, an appropriate amount of water was added to moisten the mixture, and the mixture was extruded and granulated using a small injection molding machine. After air-drying this at 30 to 60°C and crushing it, a granulator is used to
-21 to obtain granules.

Formulation Example 4 (Emulsion) Compound (31): 5 parts by weight, Compound (B): 10
Parts by weight, Tsurupol 800 A (trade name, manufactured by Toho Chemical; mixture of nonionic surfactant and anionic surfactant): 10!1 part and 5 parts by weight of 0-xylenenia were mixed and dissolved to obtain an emulsion. Ta.

Formulation Example 5 (Flowable Agent) Compound (25): 5 parts by weight, Compound (C): 10 parts by weight, Sunextract P252 (trade name, same as above) dissolved in 5 parts of water and 1 part by weight: 10 parts by weight. Kelsan S (trade name,
(manufactured by Kelco;
: 0.2 part by weight was added and mixed to obtain a flowable agent.

Test Example 1 Soil mixing treatment before rice planting (pre-emergence treatment) 1150
Fill soil in 00 Earl Wagner pot, and grow Tainubier.
Seeds of Aspergillus japonica, annual broadleaf, and firefly were sown and warm water conditions were established. A predetermined amount of the test composition was treated with an emulsion prepared according to the method described in Formulation Example 4, and the drug was mixed to a soil width of about 2 cn+. Four days later, two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. After 30 days, the growth status of weeds and the status of chemical damage to paddy rice were observed and investigated, and 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.

Growth rate (χ) shown by air drying pressure vs. untreated plot O~5
(Death) 6-10 (Quality) 11-40 (Nakayose) 41-70 (Small) 71-90 (Minor Harm) 91-100 (Harmless) Test Example 2 Flooded Soil Treatment Test (Growing Season Treatment) 11500
Soil was packed in a 0.0-R Wagner Posoto, and seeds of Japanese cabbage, Japanese cabbage, Japanese broadleaf, and bulrush were sown in warm water conditions. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. When the barnyard grass had grown to 1.5 leaves, a predetermined amount of the test composition was treated with granules prepared according to the method described in Seedling Example 3, and the growth status of weeds after 30 days was determined. We also observed and investigated the status of chemical damage to paddy rice. 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.

Test Example 3 Flooded soil treatment test (duration of effect) 115
A 000 RWagner pot was filled with soil, submerged in water, and treated with a predetermined amount of the test composition using granules prepared according to the method described in Formulation Example 3 above. The seeds of Japanese millet were sown 40 days after the treatment, and the growth status was observed and investigated 20 days later.

The results are shown in Table 4.

In the table, the degree of damage to the test plants is shown in the same manner as in Test Example 1.

Hot water soil treatment test results (sustainability of effects) Table 2.3.
As shown in 4, the herbicide composition according to the present invention can be used at any time from before rice planting to the growing season after rice transplantation to control important weeds in rice fields without harming rice. .

Furthermore, their herbicidal effects show superior synergistic action compared to each agent alone.

〔Effect of the invention〕

The herbicidal composition according to the present invention has an extremely superior herbicidal effect and duration of effect that can be expected when the pyrrolidinone derivative represented by the general formula (1) and each of the compounds A, B, and C are used alone. Due to high synergism, at lower dosages,
It has been effective against important weeds in paddy fields for a longer period of time. As a result, the herbicide composition according to the present invention can control important weeds in paddy fields for a long period of time with a single treatment, and has high applicability as a herbicide for paddy fields, and the present invention provides an extremely useful herbicide. be.

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,
4-ethyl-3-(substituted phenyl)-1-( may be different)
at least one kind of 3-trifluoromethylphenyl)-2-pyrrolidinone derivative and 2-chloro-2',6
'-Diethyl-N-(butoxymethyl)-acetanilide, 2-chloro-2',6'-diethyl-N-(n-propoxyethyl)-acetanilide or 2-chloro-
A herbicidal composition for paddy fields, characterized in that it contains at least one kind of 2',6'-dimethyl-N-(3-methoxy-2-thienyl)methylacetanilide as an active ingredient.