JPS61140504A - Herbicidal composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a herbicidal composition characterized by containing an N-substituted chloroacetanilide and a pyrazole derivative as active ingredients.

[Problem 3 to be solved by the prior art and the invention There are the following four properties that are essentially required of herbicides. That is, one, it is safe for crops, two, it has a broad herbicidal spectrum necessary to completely kill many types of weeds growing in crop-growing areas, and three.
The first is that the herbicide's efficacy lasts for a long time, and the fourth is that it has more effective herbicidal action when applied in small amounts.

The present inventors have conducted extensive research with the aim of developing an excellent herbicide that satisfies the above properties, and have obtained the following general formula CI), R% (wherein R+ is a halogen atom, an alkoxy group, an alkylthio R2 and R represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups, and R6 represents a hydrogen atom. or represents an alkyl group, R, Rh and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups,
An N-substituted chloroacetanilide represented by ) representing an alkoxy group or an alkylthio group has already been proposed (Japanese Patent Application No. 111077/1983 and others). The present inventors further provided that the N-substituted-
It has been shown that a herbicide composition containing chloroacetanilide and a specific pyrazole derivative as active ingredients exhibits a synergistic effect that could not be expected from their individual properties, that is, it has a wide herbicidal spectrum at a low dose. I found it.

Based on these new findings, the present inventors have completed and proposed the present invention.

[Means for solving problems]

The present invention is based on the following general formula CI), s (wherein R1, Rt and R5 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups or alkylthioalkyl groups). , R4 represents a hydrogen atom or an alkyl group, R5, R.

and R? represents the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups.

N-substituted-chloroacetanilide represented by represents an integer from 1 to 5, 2 represents -G ORh o or SO*R+o, and R1
゜ represents an alkyl group or a substituted or unsubstituted phenyl group, and a pyrazole derivative represented by ) as an active ingredient.

One component of the herbicide composition of the present invention is represented by the following formula -a [
It is an N-substituted-chloroacetanilide represented by I).

S A very small portion of the N-substituted-chloroacetanilides represented by the above general formula CI), that is, ThiRI is a hydrogen atom or an alkyl group, Ra, R3, and R1 are hydrogen atoms, and R3 is an alkyl group. Compounds in which R4 is a hydrogen atom, an alkyl group or an alkoxy group and R1 is a hydrogen atom, an alkyl group or a halogen atom are known from US Pat. No. 3,901,917. However, most of the others are new compounds.

In the general formula (1), RI, Rz, R3, Rs, R-
Specific examples of the halogen atom represented by and R7 include chlorine, bromine, fluorine, and iodine atoms. Furthermore, in the general formula, RI, Rz, R3, Ra, Rs
The alkyl group represented by , Ra and R1 may be linear or branched, and the number of carbon atoms is not particularly limited, but the number of carbon atoms is 1 to 6 from the viewpoint of easy availability of raw materials. It is preferable that Specific examples of the alkyl group include methyl group, ethyl group, n-propyl J! Li5o-
Examples include propyl group, n-butyl group, 1so-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and the like. In the general formula (1), R,, R,, R3, Rs,
The alkoxy group represented by R6 and R7 is not particularly limited, but a linear or branched saturated or unsaturated group having 1 to 6 carbon atoms is generally preferred. Specific examples of the alkoxy group that are generally preferably used include methoxy group, ethoxy group, n-propoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, allyloxy group, and the like.

In the general formula (1), RI, R1, Rz, Rs, R
The alkylthio group represented by 4 and R1 is not particularly limited and any known alkylthio group can be used, but it generally has 1 to 1 carbon atoms.
Six straight-chain or branched saturated or unsaturated groups are preferred. Specific examples of the alkylthio group that are preferably used include methylthio group, ethylthio group, n-propylthio group, t-butylthio group, n-pentylthio group,
Examples include n-hexylthio group and allylthio group. Further, in the above general formula, the alkoxyalkyl groups represented by Rt, Rg and R1 are not particularly limited in number of carbon atoms, but are preferably linear or branched saturated or unsaturated groups having 2 to 6 carbon atoms. Specific examples of the alkoxyalkyl group include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an n-propoxymethyl group, a t-butoxyethyl group, an allyloxyethyl group, and the like. Furthermore, in the general formula, the alkylthioalkyl group represented by R, R□ and R3 is not particularly limited in carbon number, but
Straight chain or branched saturated or unsaturated groups having 2 to 6 carbon atoms are preferred, and specific examples of the alkylthioalkyl group include methylthiomethyl group, methylthioethyl group, ethylthiomethyl group, n- Examples include propylthiomethyl group, t-butylthioethyl group, and allylthioethyl group.

Furthermore, in the general formula, the alkenyl group represented by R%, R, and R7 may be linear or branched, and the number of carbon atoms is not particularly limited. However, from the viewpoint of easy availability of raw materials, the number of carbon atoms is preferably 2 to 4. Specific examples of the alkenyl group include vinyl group, allyl 5, i! Examples include O-propenyl group, 2-butenyl group, and 3-butenyl group. In addition, in the general formula, the alkynyl group represented by Rs, Ri, and R1 has no particular restriction on the number of carbon atoms, regardless of whether it is linear or branched.
It is preferable that the number of Specific examples of the alkynyl group include ethynyl group, 2-propynyl group, and the like.

In the above N-substituted-chloroacetanilide, R7 is the same or different halogen atom, alkoxy group, alkylthio group, alkoxyalkyl group, or alkylthioalkyl group, and R2 and R8 are the same or different hydrogen atom or halogen atom. , an alkyl group, an alkoxy group, an alkylthio group, an alkoxyalkyl group, or an alkylthioalkyl group, and R4 is a hydrogen atom or an alkyl group,
For compounds in which R5, R, and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups, 15 g
Even when used at a low concentration of /10a or less, it not only has an excellent weeding effect that completely kills annual weeds such as field weeds and perennial weeds such as waterweed, but also has a high weeding effect of 500g/10a. Since it is completely harmless to rice even when used at a high concentration, it is preferably used in the present invention. In particular, at least one of RI''' R3 is a substituent other than a hydrogen atom, this substituent is substituted at the ortho position of one CH- bonded to the thiophene ring, and R4 is a hydrogen atom, Furthermore, at least two of R2-R1 are substituents other than hydrogen atoms, and N-substituted chloroacetanilide in which these substituents are substituted at the 2nd and 6th positions of the phenyl group has stronger the above properties, It is particularly preferably used.

The structure of the N-substituted chloroacetanilide represented by the general formula (I) can be confirmed by the following means.

(b) By measuring the infrared absorption spectrum (IR), it is possible to observe an absorption based on the CH bond in the vicinity of 3150-2800c+m-' and a characteristic absorption based on the carbonyl bond of the amide group in the vicinity of 1680-1660cm-'. I can do it.

(b) Measure the mass spectrum (MS) and calculate each peak observed (generally, the ion mass number m is expressed as the ion charge number e).
By calculating the composition formula corresponding to the value expressed by m/e divided by m/e, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule. That is, since the sample subjected to measurement is observed as an intensity ratio according to the isotope abundance ratio according to the number of halogen atoms of the general formula (I) s, the molecular weight of the compound subjected to measurement can be determined. Furthermore, a characteristic strong peak represented by the general formula (1) and corresponding to R8 was observed, and the bonding mode of the molecule can be known.

(c) IH-Nuclear Magnetic Resonance Spectrum (1H-NMR
), it is possible to know the bonding mode of hydrogen atoms present in the N-substituted-chloroacetanilide represented by the general formula (1). 'H-NM of N-substituted-chloroacetanilide represented by the general formula (1)
As a specific example of R (δ, ppm: based on tetramethylsilane, in deuterated chloroform solvent), N-C2''-(
'H-NMR for 5'-bromo)-thenylmethyl)-N-chloroaceto-2,6-dimethylanilide
A diagram is shown in FIG. The analysis results are as follows.

H(at H(b) CR3(
d) H(e)(h) That is, a singlet corresponding to 6 protons was observed at 2.0 ppm, and this is attributed to the methyl group (d) substituted at the 2 and 6 positions of the phenyl group. can. 3.6
A singlet corresponding to two protons was observed in ppa+, and this can be attributed to methylene i (h) in the chloroacetyl group. A singlet corresponding to two protons was observed at 4.75 ppn+, and this can be attributed to the methylene group (C). A quartet corresponding to two protons was observed at 6.67 pP-, and this can be attributed to protons (a) and (b) substituted on the thiophene ring. A multiplet corresponding to three protons was observed at 6.95 to 7.30 ppm, and this can be attributed to the protons (e), (f), and (Xi) substituted with phenyl groups.

Summarizing the 'H-NMR characteristics of the N-substituted-chloroacetanilide represented by the above-mentioned general formula CI), the methylene proton of the chloroacetyl group is usually 3.6 to 3.8
Appears as a singlet near ppm, and when R4 is a hydrogen atom, the methylene proton of the aminomethylene group is 4.7~
5. A single line near Oppm (however, if there is an asymmetric substituent at the 2.6-position on the aniline side, a double line may appear), and if R4 is an alkyl group, aminomethine The methine proton of the group is 5.7~
6.7 ppm, and the proton on the thiophene ring side is 5.8
~7.4ppm, and the protons on the benzene side are 6.0~7
．． It tends to show a characteristic peak at 7 ppm.

(d) The weight percent of oxygen can be calculated by determining the weight percent of carbon, hydrogen, nitrogen, sulfur, and halogen by elemental analysis, and then subtracting the sum of the weight percent of each recognized element from 100. Therefore, the compositional formula can be determined.

In addition, N-substituted-chloroacetanilide includes R+, Rz, R3, R4, R2, Rh, and R in the general formula (1).
Although its properties differ somewhat depending on the type of 7, it is generally a pale yellow or yellow viscous liquid or solid at room temperature and normal pressure, and many have extremely high boiling points.Specifically, they are shown in the synthesis examples below. As with general organic compounds, the boiling point of the above compound tends to increase as the molecular weight increases.
It is soluble in general organic solvents such as , N-dimethylformamide and dimethyl sulfoxide, but almost insoluble in water.

The method for producing the N-substituted-chloroacetanilide represented by the general formula (1) is not particularly limited. A typical manufacturing method is described below. General formula % formula %) (However, in the formula, R+, Rz and R1 represent the same or different hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, alkoxyalkyl group or alkylthioalkyl group, and R4 is a hydrogen atom or represents an alkyl group, R6, R8 and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups,
Alkoxy group 1. Or represents an alkylthio group. ) and the general formula CI G Hz
By reacting with chloroacetyl halide represented by COX (where X represents a halogen atom), the N-substituted-chloroacetanilide represented by the general formula (I) can be obtained.

The aniline derivative represented by the general formula (III) as a raw material can be obtained by any method.

In the reaction between the compound represented by the general formula (III) and chloroacetyl halide, the molar ratio of both compounds to be charged may be appropriately determined as necessary, but it is usually the same molar ratio or a slight excess molar amount of chloroacetyl halide. It is common to use

Further, in the above reaction, hydrogen halide is produced as a by-product. Since this hydrogen halide reacts with the aniline derivative represented by the general formula (III) in the reaction system and causes a decrease in the yield of the product, a hydrogen halide scavenger is usually coexisted in the reaction system. It is preferable. The hydrogen halide scavenger is not particularly limited, and any known one can be used.

Examples of the scavenger that are generally suitably used include trialkylamines such as trimethylamine, triethylamine, and tripropylamine, pyridine, sodium alcoholade, and sodium carbonate.

It is generally preferable to use an organic solvent in the reaction. Examples of solvents that are preferably used include:
Benzene, toluene, xylene, hexane, heptane,
Aliphatic or aromatic hydrocarbons or halogenated hydrocarbons such as petroleum ether, chloroform, methylene chloride, and ethylene chloride; ethers such as diethyl ether, dioxane, and tetrahydrofuran; ketone necks such as acetone and methyl ethyl ketone; acetonitrile, etc. Nitriles iN, N-dialkylamides such as N-dimethylformamide and N,N-diethylformamide; dimethyl sulfoxide and the like.

The order of addition of the raw materials in the reaction is not particularly limited, but generally, the aniline derivative represented by the general formula CDI) is dissolved in a solvent, charged into a reactor, and the chloroacetyl halide dissolved in the solvent is added under stirring. It is better.

Of course, it is also possible to continuously add raw materials to the reaction system and take out the produced reactants continuously from the reaction system.

The temperature for the above reaction can be selected from a wide range, and generally it is sufficient to select it from the range of -20°C to 150°C, preferably 0°C to 120°C.The reaction time varies depending on the type of raw materials, but is usually 5 minutes to lO days, preferably 1-40
It is sufficient to choose from the time range. Further, during the reaction, it is preferable to perform stirring.

The method for isolating and purifying the desired product, ie, the N-substituted-chloroacetanilide represented by the general formula CI) from the reaction system, is not particularly limited and any known method can be employed. For example, the reaction solution is cooled or allowed to cool naturally to return to room temperature or near room temperature, the reaction solvent and the remaining hydrogen halide scavenger are distilled off, and the residue is extracted with benzene. In the above operation, the salt and high molecular weight compound produced from the by-produced hydrogen halide and the hydrogen halide scavenger are separated. The benzene layer is dried with a desiccant such as Glauber's salt or calcium chloride, and then benzene is distilled off and the residue is vacuum distilled to obtain the desired product. In addition to producing a single crystal by vacuum distillation, it can also be purified by chromatography or, if the product is a solid, by recrystallization from a solvent such as hexane.

As another method for producing the N-fi-substituted chloroacetanilide represented by the general formula (1), the following method is also preferably employed.

General formula (wherein R+, Rz and R1 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, alkylthioalkyl groups, and R1 represents a hydrogen atom or an alkyl group) show,
X represents a halogen atom. ) and a substituted thiophene represented by the general formula (wherein Rs, R& and R7 represent the same or different hydrogen atoms, halogen atoms, aalkoxy groups, and alkylthio groups.

) by reacting with chloroacetanilide represented by the formula (1).
Chloroacetanilide can be obtained.

The substituted thiophene and the chloroacetanilide used as raw materials can be obtained by any method.

In addition, the conditions and isolation and purification method for carrying out this reaction are almost the same as those used in the reaction of the aniline derivative represented by the general formula CIIF) with chloroacetyl halide as described above. The N-1i-chloroacetanilide represented by the above general formula (1), which can be used under the following conditions, is effective against a wide range of annual weeds such as Japanese grasshopper, Japanese grasshopper, and scallops that occur in rice fields, as well as perennial weeds such as Cyperus japonica and Omodaka. It is an excellent herbicide that has a herbicidal spectrum and can efficiently control paddy rice without causing chemical damage.

The other component of the herbicidal composition of the present invention has the following general formula [■] Bone R1 (wherein R11 and R are the same or different hydrogen atoms or alkyl groups, and Y is a hydrogen atom, a halogen atom, or an alkyl group). or a nitro group, n represents an integer from 1 to 5, Z represents -COR, or -3OzR+o, RIG
represents an alkyl group or a substituted or unsubstituted phenyl group. ) is a pyrazole derivative represented by

In the above general formula (II), Rs, Rq, Rt. The alkyl group represented by , and Y is not particularly limited in its carbon number, and any alkyl group can be used. Among these, those having 1 to 4 carbon atoms are preferred. Preferred alkyl groups in the present invention include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i -butyl group, 5
Examples include ec-butyl group and t-butyl group. Also,
In the above general formula (II), examples of the halogen atom represented by Y include stratum corneum of fluorine, chlorine, bromine, and iodine. Furthermore, in the general formula (n), Ro. Examples of the substituted phenyl group represented by include those substituted with one or more substituents such as halogen atoms or alkyl groups. The halogen atom and alkyl group substituted on the phenyl group are as described above. Preferred substituted phenyl groups in the present invention include tolyl group, ethylphenyl Li-propylphenyl group, t-butylphenyl group, dimethylphenyl group, diethylphenyl group, ethyltolyl group, trimethylphenyl group, triethylphenyl group, Chlorphenyl group, fluorophenyl group, bromphenyl group, iodophenyl group, dichlorophenyl group,
Examples include dibromphenyl group, trifluorophenyl group, trichlorophenyl group, methyldichlorophenyl group, ethyldibromophenyl group, methyltrichlorophenyl group, among others, compounds in which at least one substituent is substituted at the p-position. is particularly preferred.

Among the pyrazole derivatives represented by the above general formula (II), R1 and R9 are alkyl groups, particularly methyl groups, and Y
Compounds in which halogen atoms, particularly chlorine, are substituted at the 2 and 4 positions of the phenyl group are preferably used because they have little phytotoxicity and high herbicidal activity.

As the method for producing the pyrazole derivative represented by the above general formula (II), any known production method may be employed without any restriction.

The pyrazole derivative represented by the general formula (n) is known to induce chlorosis by photooxidation of chlorophyll based on inhibition of carotenoid biosynthesis, and is highly effective against broad-leaved weeds including perennial weeds. Although it has an extremely high herbicidal effect on weeds such as grasshoppers and weeds, it has a weak effect on weeds such as field weeds and weeds.

The herbicidal composition of the present invention exhibits excellent herbicidal effects over a wide range of usage ratios of the N-substituted chloroacetanilide represented by the general formula (1) and the pyrazole derivative represented by the general formula (n). It will be done. However, the ratio of the pyrazole derivative to 1 part by weight of the N-substituted chloroacetanilide is generally in the range of 0.01 to 50 parts by weight. More preferably, by using 1 to 20 parts by weight of the pyrazole derivative per 1 part by weight of the N-substituted to chloroacetanilide, the herbicidal effect becomes even more excellent.

When the herbicide composition of the present invention is used against wildflowers and paddy rice that are sown at the same time in paddy soil, 0.1 per are
When treated at a concentration of 100 g, germination of wild grass is completely inhibited, but paddy rice is not affected at all even when treated at 100 g.

Therefore, it is generally sufficient to use the active ingredient in rice fields in an amount of 0.15 to 200 g, preferably 0.5 to 50 g per are.

The herbicide composition of the present invention is effective even when treated before and after weed germination, and is highly effective in soil treatment and foliage treatment. It is useful in a wide range of areas where it can be applied, including rice fields, fields of various grains, legumes, cotton, vegetable crops, orchards, lawns, pastures, tea gardens, mulberry gardens, forests, non-agricultural lands, etc. .

The herbicidal composition of the present invention may be sprayed as a raw material itself, or may be sprayed as a preparation prepared by mixing with a carrier and other adjuvants if necessary, and there are no particular restrictions on the formulation form. First, conventionally known formulations are used. For example, powder
It can be prepared and used in coarse powders, fine granules, granules, wettable powders, emulsions, flowable preparations, oil suspensions, etc.

When preparing the herbicidal composition of the present invention into a formulation, conventionally known solid carriers can be used without any limitations as suitable solid carriers.

Examples of solid carriers preferably used in the present invention are as follows. For example, clays represented by kaolinite group, montmorillonite group, attapulgite group, or gicrite; talc, mica, phyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, magnesium diatomaceous earth, lime, phosphoric acid. Inorganic substances such as stone, zeolite, silicic anhydride, and synthetic calcium silicate;
Vegetable organic substances such as soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose; coumaron resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal gum , synthetic or natural polymer compounds such as dammargum, waxes such as carnauba wax and beeswax, or urea.

Further, as the liquid carrier used in the present invention, conventionally known carriers can be used without any restriction. Examples of liquid carriers preferably used in the present invention are as follows. Paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil; benzene, toluene, xylene, ethylbenzene, cumene,
Aromatic hydrocarbons such as methylnaphthalene; chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, monochlorobenzene, 0-chlorotoluene; ethers such as dioxane and tetrahydrofuran; acetone,
Ketones such as methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; Esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, n
-Alcohols such as hexanol, ethylene glycol and diethylene glycol; ether alcohols such as ethylene glycol phenyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide; and water.

Furthermore, in the preparation of the formulation in the present invention, conventionally known surfactants are used for the purposes of emulsification, dispersion, wetting, spreading, binding, disintegration control, active ingredient stabilization, flowability improvement, rust prevention, etc. It can be used without any restrictions. As surfactants, nonionic,
Although cationic, anionic and amphoteric ones are used, nonionic and/or anionic ones are usually preferred. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; those obtained by polymerizing and adding ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol: Products in which ethylene oxide is polymerized and added to alkylphenols such as isooctylphenol and nonylphenol; Products in which ethylene oxide is polymerized and added to alkylnaphthols such as butylnaphthol, octyl, and naphthol; Ethylene oxide is added to higher fatty acids such as valmitic acid, stearic acid, and oleic acid. Polymerized addition products: Mono- or dialkyl phosphoric acids such as stearyl phosphoric acid and dilauryl phosphoric acid and ethylene oxide added to them; Dodecylamine and amines such as stearic acid amide and ethylene oxide added to them by polymerization; Sorbitan, etc. Examples include higher fatty acid esters of polyhydric alcohols and those obtained by polymerizing and adding ethylene oxide to them; those obtained by polymerizing and adding ethylene oxide and propylene oxide; and esters of polyhydric fatty acids and alcohols such as dioctyl succinate. Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt; alkyl sulfonate salts such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulfonate. ;
Aryl sulfonates such as sodium isopropylnaphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzenesulfonate; phosphates such as sodium tripolyphosphate; and the like.

Furthermore, in the formulation of the present invention, conventionally known adjuvants can be used without any restrictions. Adjuvants are used for various purposes, and are also used, for example, when attempting to enhance the herbicidal effect by improving properties such as disintegration of granules. Examples of adjuvants suitably used in the present invention are as follows.

Examples include high molecular compounds such as casein, gelatin, albumin, glue, sodium ruginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol.

The above-mentioned carriers, surfactants and adjuvants are suitable for the dosage form of the preparation,
They are used individually or in combination as appropriate depending on the purpose, taking into consideration the application situation.

The method for preparing the formulation in the present invention is not particularly limited (any conventionally known method may be used. For example, as a specific method for preparing a hydrating powder, pyrazole derivative 10
There is a method of obtaining a wettable powder by dissolving 1 part by weight of N-substituted chloroacetanilide in an organic solvent, adding a surfactant and a carrier to the solution, pulverizing and mixing thoroughly, and then removing the organic solvent.

For example, as a specific method for preparing an emulsion, 10 parts by weight of a pyrazole derivative, 5 parts by weight of N-substituted chloroacetanilide, and 15 parts by weight of a surfactant are thoroughly mixed in a petroleum solvent such as xylene to obtain an emulsion. There is a way.

Furthermore, as a specific method for preparing granules, for example, 10 parts by weight of a pyrazole derivative, 1 part by weight of N-substituted chloroacetanilide, a surfactant and water are thoroughly kneaded,
Next, there is a method of obtaining granules by adding a carrier and a surfactant, stirring well, extruding to a predetermined particle size, and drying.

〔effect〕

The herbicidal composition of the present invention described above exhibits a herbicidal effect that cannot be expected from the properties of each component alone. That is, the herbicidal composition of the present invention exhibits an excellent herbicidal effect against perennial weeds such as cypress, for which neither the N-substituted-chloroacetanilide nor the pyrazole derivative can be expected to have much herbicidal effect when used alone. Demonstrate.

Therefore, the herbicidal composition of the present invention has a broader herbicidal spectrum than that of its constituent components alone.

Furthermore, it has a greater herbicidal effect at the same level as the application amount of each component alone. Moreover, it is safe for crops.

Therefore, the herbicidal composition of the present invention fully satisfies the properties required of a herbicide, and is extremely useful.

EXAMPLES The herbicidal composition of the present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

N--Structure of chloroacetanilide- (Synthesis Example 1) N-(2'-(5°-bromo)-chenylmethyl)-
2,6-dimethylaniline 1,81 g (6,14X
10-"n+ole) was dissolved in 40 mIt of benzene and 0.81 g of triethylamine (7,98X 1
0-3 mole) and placed in ice water. Then 0.83 g of chloroacetyl chloride (7,37X 1
A benzene solution (15ml) of 0-"++ole) was added slowly.

After stirring for 3 hours, the mixture was heated at 50°C for 1 hour. After cooling the reaction mixture to room temperature, 50 ml of water, 50 ml of 2N-hydrochloric acid
The benzene layer was washed with 50 ml of water, and the benzene layer was dried over anhydrous sodium sulfate. Thereafter, it was purified by column chromatography to obtain 1.13 g of a yellow solid. As a result of measuring the infrared absorption spectrum of this material, it was found that 3110-29
Absorption based on C-H bond at 00cm-', 1670co
Strong absorption based on 5 carbonyl bonds of the amide group was shown at +-'. Its elemental analysis values are C4B, 43%, H4.0
5%, N3.99%, C+sH'tsNSOB
, , C4 is the calculated value for Cl1 (372,71)
It was in good agreement with 8.20%, H4, 32%, and N3.75%.

In addition, when we measured the mass spectrum, m/e143
Each peak corresponding to (100%) is shown.

Furthermore, 1) (-Nuclear magnetic resonance spectrum is as shown as a specific example in the specification.

From the above results, it is clear that the isolated product is
-Simethylanilide (hereinafter abbreviated as compound (1))
It became clear that. The yield is N-(2'-(5
49.5% (3,04X 10-3+o
ole).

(Synthesis Example 2) The properties, physical properties (boiling point), characteristic absorption values in the infrared absorption spectrum, and elemental analysis results of N-substituted-chloroacetanilide synthesized in the same manner as in Synthesis Example 1 are summarized in Table 1.

Furthermore, the general formula in Table 1 %formula% is the above general formula (1) means.

Next, formulation examples and examples of the herbicide composition of the present invention will be shown. In addition, in the formulation examples and examples, N-substituted-chloroacetanilide is the compound number in the synthesis side [(1) to (66)
), and pyrazole derivatives are represented by the following symbols ([A] ~
[M]).

Formulation example 1 10 parts by weight of compound (A), 5 parts by weight of compound (1), surfactant Tsurupol 800A (Toho Chemical Industries ■trademark) 1.
A wettable powder was obtained by thoroughly pulverizing and mixing 5 parts by weight of the surfactant Detardient 60 (Lion Oil ■ Trademark) and 82 parts by weight of Zikrite.

Formulation example 2 20 parts by weight of compound (A), 10 parts by weight of compound (17),
15 parts by weight of the surfactant Tsurupol 5M100 (trademark of Toho Chemical Industries) and 55 parts by weight of xylene were thoroughly mixed to obtain an emulsion.

- Formulation example 3 10 parts by weight of compound (A), 1 part by weight of compound (39), 4 parts by weight of dioctyl succinate, 4 parts by weight of sodium tripolyphosphate, 41 parts by weight of bentonite, and 4 parts by weight of talc.
0 parts by weight were thoroughly mixed and pulverized, water was added and kneaded, and then granulated and dried, and the particles were sized to 14 to 32 meshes to obtain granules.

Formulation Example 4 40 parts by weight of bentonite, 55 parts by weight of talc, and 5 parts by weight of sodium tripolyphosphate are ground and mixed, added with water, kneaded, and then granulated and dried to produce granules containing no active ingredient. 10 parts by weight of compound (A) and 5 parts by weight of compound (40) were impregnated into 85 parts by weight of the granules to obtain granules.

Example 1 A Wagner pot equivalent to 1/5000 are was filled with water-mixed paddy soil, and seeds of broad-leaved weeds such as Japanese grasshopper, Japanese cypress, Japanese firefly, and broad-leaved weeds such as Japanese grasshopper, Japanese cypress, and Japanese cypress were sown on the soil surface. embedded with tubers. Furthermore, three rice seedlings (variety name: Akinishiki) at the 2.5-leaf stage were planted at a depth of 2 cm. after that,
Grow in a glass room at 20-25℃ under warm water conditions of about 3 cm, and 7 days after transplanting the rice (when the wildflowers are at about 0.8 leaf stage)
After 14 days (when the wildflowers were at about the 2-leaf stage), the wettable powder prepared according to Formulation Example 1 was diluted with water and a predetermined amount was dropped. Thereafter, the plants were grown in a glass room, and on the 21st day after the chemical treatment, the herbicidal effect and the chemical damage to paddy rice were investigated. The results are shown in Table 2.

Weeding effect Paddy rice chemical damage weed suppression rate (%) -: Normal 5: 100 (complete withering) ±: Small diameter small 4 near 5-9
9 +: Minor damage 3: 50-74
廿: Nakayori 2: 25-49 1: 1-24 0: 0 (no effect observed at all)

[Brief explanation of drawings]

FIG. 1 shows a 'H-NMR chart of N-substituted-chloroacetanilide obtained in Synthesis Example 1.

Claims (1)

[Claims] The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Represents an alkyl group or an alkylthioalkyl group, R_4 represents a hydrogen atom or an alkyl group, and R_5, R_6, and R_7 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio (indicates a group.) N-substituted-chloroacetanilide represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_8 and R_9 are the same or different hydrogen atoms or alkyl groups, and Y is hydrogen represents an atom, a halogen atom, an alkyl group, or a nitro group, n represents an integer from 1 to 5, Z represents -COR_1_0 or -SO_2R_1_0, and R_1_0 represents an alkyl group or a substituted or unsubstituted phenyl group.) A herbicidal composition comprising a pyrazole derivative represented by the following as an active ingredient.