JPS61143308A - herbicide 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 sulfonylurea 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 developed the following general formula (where R is a halogen atom, an alkoxy group, an alkylthio group, an alkoxyalkyl or an alkylthioalkyl group, R2 and R1 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups, and R4 represents a hydrogen atom or an alkyl group. , Rs, Rh and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups,
Indicates an alkoxy group or an alkylthio group. ) have already been proposed (Japanese Patent Application No. 58-111077 and others). The present inventors further discovered that a herbicide composition containing an N-substituted chloroacetanilide represented by the above general formula and a specific sulfonylurea derivative as active ingredients has a synergistic effect that could not be expected from the properties of each alone. To manifest an effect, that is,
It was found that it has a wide herbicidal spectrum at low doses.

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 (I), (wherein R+, Rz and R1 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, and R5, R6, and R7 represent the same or different hydrogen atoms, halogen atoms, alkynyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups.

N-substituted-chloroacetanilide represented by the following general formula (U) R1 iris

R6 (However, in the formula, R8 and R9 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, or alkoxy groups, R1° represents a hydrogen atom, alkyl group, or alkoxy group, and R8, RI!, and R+3 are the same or a different hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxysulfonyloxy group, an alkylsulfonyloxy group, or a carboxylic acid group or an ester group thereof, Y represents an oxygen atom or an alkylene group, and Z represents a nitrogen atom or (a methine group, n is 0 or 1).

One component of the herbicidal composition of the present invention has the following general formula C
It is an N-substituted monochloroacetanilide represented by I).

(However, in the formula, R,, R2 and R3 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups, and R4 represents a hydrogen atom or an alkyl group. and R5%R6 and R7 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups.) N-substituted- represented by the above general formula [I] A small portion of chloroacetanilide, i.e. 2 of the thiophene ring
position and -CH- are bonded, R1 is a hydrogen atom or an alkyl group, R,, R3 and R4 are hydrogen atoms, and R
5 is an alkyl group, R6 is a hydrogen atom, an alkyl group, or an alkoxy group, and R? is a hydrogen atom, an alkyl group, or a halogen atom, as disclosed in U.S. Pat. No. 390
No. 1917. However, most of the others are new compounds.

Specific examples of the halogen atoms represented by RI, R2, R3, R6, R4, and R1 in the general formula CI) include chlorine, bromine, fluorine, and iodine atoms. Also,
In the general formula, R3, Rz, Rs, Ra, Rs,
The alkyl group represented by Rh and R1 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 1 to 6. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 1so-butyl group, L-butyl group, n-pentyl group, n-hexyl group. etc.

In the general formula (I), the alkoxy groups represented by R, R2, R3, R2, R6 and R1 are not particularly limited, but
In general, linear or branched saturated or unsaturated groups having 1 to 6 carbon atoms are 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), R1, R2, R3, Rs, R, and R? The alkylthio group represented by is not particularly limited and any known alkylthio group can be used, but a linear or branched saturated or unsaturated group having 1 to 6 carbon atoms is generally preferred. Specific examples of the alkylthio group suitably used include methylthio group, ethylthio group, n-propylthio group, t-butylthio group, n-pentylthio group, n-
Examples include hexylthio group and allylthio group. Also,
In the general formula, the alkoxyalkyl group represented by R, R2 and R3 is not particularly limited in number of carbon atoms, but
~6 linear or branched saturated or unsaturated groups are preferred; specific examples of the alkoxyalkyl group include methoxymethyl group, methoxyethyl group, ethoxymethyl group, n-propoxymethyl group; , t-butoxyethyl group, allyloxyethyl group, and the like. Furthermore, in the general formula, the alkylthioalkyl group represented by R, R2 and R3 is not particularly limited in the number of carbon atoms, but is preferably a linear or branched saturated or unsaturated group having 2 to 6 carbon atoms. Specific examples of the alkylthioalkyl group include methylthiomethyl group, methylthionityl group, and ethylthiomethyl! , n-propylthiomethyl group, t
-butylthioethyl group, allylthioethyl group, etc.

Furthermore, in the above general formula, the alkenyl groups represented by Rs, Rh, 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, it is preferable that the number of carbon atoms is 2 to 4. Specific examples of the alkenyl group include vinyl group, allyl group, 1so-
Examples include propenyl group, 2-butenyl group, 3-butenyl group, and the like. In addition, in the general formula, the alkynyl group represented by Rs, Rh, and R7 may be linear or branched, and the number of carbon atoms is not particularly limited.
It is preferable that the number is four. Specific examples of the alkynyl group include ethynyl group, 2-propynyl group, and the like.

In the above N-substituted-chloroacetanilide, R1 is a halogen atom, an alkoxy group, an alkylthio group, an alkoxyalkyl group, or an alkylthioalkyl group,
R2 and R3 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups,
R4 is a hydrogen atom or an alkyl group, and Rs, Rh, 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 water cypress, but also at a high concentration of 500g/10a. Since it is completely harmless to rice when used, it is suitably used in the present invention. In particular, at least one of R1-R8 is a substituent other than a hydrogen atom, this substituent is substituted at the ortho position of 10H- bonded to the thiophene ring, and R4 is a hydrogen atom, Furthermore, out of R6-R9, a small number (two of them 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 properties as described above. , is particularly preferably used.

The structure of the N-substituted-chloroacetanilide represented by the general formula CI) 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 near 3150 to 2800 cm-' and a characteristic absorption based on the carbonyl bond of the amide group near 1680 to 1660 cm+-'. .

(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. In other words, the general formula (1) (hereinafter abbreviated as M) of the sample subjected to measurement is observed as an intensity ratio according to the isotope abundance ratio depending on the number of halogen atoms contained in the molecule. The molecular weight of the compound can be determined. Furthermore, for the N-substituted-chloroacetanilide represented by the general formula [1], characteristic strong peaks corresponding to M C1, M C0CHzCIt and R1 were observed, which revealed the bonding mode of the molecule. I can know.

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

H(a) H(b) CH
3(d) H(el(hl) In other words, a singlet corresponding to 6 protons was observed at 2.0 ppm, and this can be attributed to the methyl group (dl) substituted at the 2 and 6 positions of the phenyl group. .3.6
A singlet corresponding to two protons was observed in ppta, and this can be attributed to methylene 5 (hl) in the chloroacetyl group.A singlet corresponding to two protons was observed at 4.75 ppm. This is a methylene group (C
). A quartet corresponding to two protons was observed at 6.67 ppm, and this can be attributed to protons (al and (bl) substituted on the thiophene ring. At 6.95 to 7.30 ppm, a quartet corresponding to two protons was observed. A corresponding multiplet was observed, which can be attributed to the protons (el, (f), (g)) substituted on the phenyl group.

Summarizing the 'H-NMR characteristics of the N-substituted-chloroacetanilide represented by the general formula (1) above, 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~
5.7 ppm, and the proton on the thiophene ring side is 5.8
~7.4 ppm, and protons on the benzene side are ~6.0
It tends to show a characteristic peak at 7.7 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 R1, R2, R3, R1, R6, R6 and R
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. The specific details will be shown in the synthesis examples described later, but the boiling point of the above compound tends to increase as the molecular weight increases, as with general batter compounds. The compounds include benzene, ether, alcohol, chloroform, carbon tetrachloride, acetonitrile, N,
It is soluble in general organic solvents such as N-dimethylformamide and dimethyl sulfoxide, but is hardly soluble in water? I can't stand it.

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, R9, Rh and R7 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups,
Indicates an alkoxy group or an alkylthio group. ) Aniline derivatives represented by the general formula 〇lCH2CO
By reacting with chloroacetyl halide represented by

The aniline derivative represented by the general formula [I[1] 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. This hydrogen halide reacts with the aniline derivative represented by the general formula [m] in the reaction system, causing a decrease in the yield of the product, so 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; ketones such as acetone and methyl ethyl ketone; Nitrile '114; N, N'; Methylformamide,
Examples include N,N-dialkylamides such as N,N-diethylformamide; dimethylsulfoxide, and the like.

The order of addition of raw materials in the reaction is not particularly limited, but generally, the aniline derivative represented by the general formula [111] is dissolved in a solvent, the mixture is 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 in 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 θ°C to 120°C. The reaction time varies depending on the type of raw material, but is usually 5 minutes to IO days, preferably 1 to 40 days.
It is sufficient to choose from the time range. It is also preferable to stir the reaction mixture during the reaction.

The method for isolating and purifying the target product, ie, the N-substituted-chloroacetanilide represented by the general formula (1), 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 salts and high molecular weight compounds generated from the by-produced hydrogen halide and the hydrogen halide scavenger are separated.The benzene layer is dried with a desiccant such as mirabilite or calcium chloride, and then the benzene is removed. The desired product is obtained by distilling off the residue and vacuum distilling the residue. In addition to isolation and purification 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-substituted-chloroacetanilide represented by the general formula CI), the following method is also preferably employed.

General formula (wherein R, , R, and R8 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, and alkylthioalkyl groups, and R4 represents a hydrogen atom or an alkyl Indicates the group,
X represents a halogen atom. ) and a substituted thiophene represented by the general formula (wherein R5, R6 and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups,
The N-substituted chloroacetanilide represented by the above general formula [■] can also be obtained by reacting with a chloroacetanilide represented by , ) representing an alkoxy group or an alkylthio group.

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 (III) and chloroacetyl halide as described above. The N-substituted-chloroacetanilide represented by the above general formula (I), which can be applied under similar conditions, is effective against weeds of 4m per year, such as wild grass, bulrush, and cypress, which occur in rice fields, as well as perennial weeds, such as Omodaka. It is an excellent herbicide that has a wide herbicidal spectrum and can efficiently control paddy rice without causing chemical damage.

The other component of the herbicide composition of the present invention is represented by the following general formula (n)
, RII R8
(However, in the formula, R1 and R9 are the same or different hydrogen atoms,
Represents a halogen atom, alkyl group or alkoxy group, R
ho represents a hydrogen atom, an alkyl group or an alkoxy group,
R1R, □ and R13 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxysulfonyloxy groups, alkylsulfonyloxy groups, carboxylic acid groups or ester groups thereof, and Y is an oxygen atom or alkylene group, Z represents a nitrogen atom or a methine group, and n represents 0 or 1. ) is a sulfonylurea derivative represented by

In the above general formula (II), R8, R9, R10, Ro, R
The alkyl group represented by 1□ and R13 is not particularly limited in its carbon number, and any group can be used.

Among these, those having 1 to 4 carbon atoms are preferred. Suitable alkyl groups in the present invention include methyl group, ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
Examples include butyl group, 5ec-butyl group, t-butyl group, and the like.

Furthermore, in the general formula (n), Ra, Rq, R8, R1
Examples of the halogen atom represented by □ and RI3 include fluorine, chlorine, bromine, and iodine atoms. moreover,
Also, in the general formula (II) above, Rs, , R9, R+. R1
As the alkoxy group represented by R+z and RI3,
Again, the number of carbon atoms is not particularly limited, but those having 1 to 5 carbon atoms are preferred from the viewpoint of easy availability of raw materials. Suitable alkoxy groups in the present invention include methoxy group, engineered toxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentoxy group, etc. It will be done.

Furthermore, in the above general formula (II), the ester group of the carboxylic acid represented by R11, R52 and R1ff is not particularly limited, but an alkyl ester group is suitable. As for the alkyl group contained in the alkyl ester group and alkylsulfonyloxy group, the alkyl groups described above are used.

Further, in the general formula, the alkylene group represented by Y 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, it is preferable that the number of carbon atoms is 1 to 4. Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and the like.

Among the sulfonylurea derivatives represented by the above general formula CUE, R11 and R9 are alkoxy groups, especially methoxy groups, R1°, R11 and R12 are hydrogen atoms, and R
Compounds in which 13 is a carboxylic acid alkyl ester group substituted at the ortho position of a phenyl group, especially a carboxylic acid methyl ester group, Y is a methylene group, Z is a methine group, and n is 1, have less drug toxicity. , is preferably used because of its high herbicidal activity.

As the method for producing the sulfonylurea derivative represented by the above general formula (n), any known production method can be employed without any restriction.

The sulfonylurea derivative represented by the above general formula (II) has a high herbicidal effect on annual broad-leaved weeds such as cypress, cypress, and cyperus, as well as perennial weeds such as scallops. However, it has a property that it has a slightly low herbicidal effect on grass weeds such as field grass.

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 [I] and the sulfonylurea derivative represented by the general formula (II). can get. However, the ratio of the sulfonylurea derivative to 1 part by weight of N-substituted chloroacetanilide is 0.01 part by weight.
It is generally in the range of ~50 parts by weight. More preferably, the herbicidal effect becomes even more excellent by using the sulfonylurea derivative in an amount of 0.1 to 10 parts by weight per 1 part by weight of the N-substituted chloroacetanilide.

When the herbicide composition of the present invention is used against wildflowers and paddy rice that are sown in paddy soil at the same time, o per are,
When treated with a concentration of 1 g, the germination of wild plants is completely inhibited, but paddy rice is not affected at all even when treated with 100 g. Therefore, generally 0.10 to 200g per are,
Preferably, it may be used in paddy fields in an amount of 0.3 to 50 g of active ingredient.

The herbicide composition of the present invention is effective even when treated before and after weed germination, and the weeding effect can also be obtained 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 it with a carrier and, if necessary, other adjuvants. The formulation form is not particularly limited, and conventionally known formulation forms can be used. For example, it can be prepared and used in powders, coarse powders, fine granules, granules, wettable powders, emulsions, flowable preparations, oil suspensions, and the like.

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, diatomaceous earth, magnesium, lime, phosphorus. Inorganic substances such as scheelite, zeolite, silicic anhydride, and synthetic calcium silicate; Vegetable organic substances such as soybean flour, tobacco powder, walnut flour, wheat flour, wood flour, starch, and crystalline cellulose; Coumaron resin, petroleum resin, and alkyds Synthetic or natural polymer compounds such as resins, polyvinyl chloride, polyalkylene glycols, ketone'tM fats, ester gums, copal gums, and dammar gums; waxes such as carnauba wax and beeswax; and 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, and 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,
Examples include alcohols such as n-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; Polymerization of ethylene oxide to alkyl phenols such as isooctylphenol and nonylphenol; Polymerization of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Polymerization of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid. Added: stearyl phosphate,
Dilauryl phosphoric acid is also obtained by polymerizing and adding ethylene oxide to mono- or dialkyl phosphoric acid; ethylene oxide is polymerizing and adding to amines such as dodecylamine and stearic acid amide; higher fatty acid esters of polyhydric alcohols such as sorbitan and ethylene oxide are added to them. Polymerization addition products; polymerization addition products of ethylene oxide and propylene oxide; esters of polyhydric fatty acids such as dioctyl succinate and alcohols, and the like. 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 isopropylnaphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylhenzenesulfonate; and phosphates such as sodium tripolyphosphate.

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 alginate, 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, and conventionally known methods can be used. For example, as a specific method for preparing a wettable powder, 5 parts by weight of a sulfonylurea derivative and 25 parts by weight of N-substituted chloroacetanilide were dissolved in an organic solvent, and a surfactant and a carrier were added to the solution and thoroughly ground and mixed. After that, there is a method of obtaining a hydrating agent by removing the organic solvent.

For example, as a specific method for preparing an emulsion, 5 parts by weight of a sulfonylurea derivative, 25 parts by weight of N-substituted chloroacetanilide, and 5 parts by weight of a surfactant are thoroughly mixed in an organic solvent such as dimethylformamide to prepare an emulsion. There is a way to get it.

Furthermore, for example, as a specific method for preparing granules, 0.15 parts by weight of a sulfonylurea derivative, N-substituted-
Thoroughly knead 0.75 parts by weight of chloroacetanilide, a surfactant and water, then add a carrier and a surfactant,
There is a method of obtaining granules by 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. In other words, the herbicide composition of the present invention is effective against perennial weeds such as staghorn snail and snail, for which a complete herbicidal effect cannot be expected when either N-M-chloroacetanilide or sulfonylurea derivatives are used alone. The product exhibits excellent weeding effects. Therefore, the herbicidal composition of the present invention has a broader herbicidal spectrum than that of its constituent components alone, and has a greater herbicidal effect. Furthermore, 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.

Synthesis of N-1-chloroacetanilide J (Synthesis Example 1) N-(2'-(5''-bromo)-chenylmethyl)-
1.81 g of 2,6-dimethylaniline (6,14X
10-"mole) in 40ml of benzea and 0.81g of triethylamine (7,98X 10-3mol)
le) and placed in ice water. Then 0.83 g of chloroacetyl chloride (7,37X 10-3 mo
A benzene solution (15 mL) of LE) was gradually added.

After stirring for 3 hours, the mixture was heated at 50°C for 1 hour. After cooling the reaction mixture to room temperature, 50 mi! of water was added. , 2N-hydrochloric acid 5
0mj2. Subsequently, the mixture was washed successively with 50 ml of water, and the benzene layer was dried over anhydrous sodium farate. 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, 3110
Absorption based on C-H bond at ~2900 cm-', 167
A strong absorption based on the carbonyl bond of the amide group was observed at 0 cm-'. Its elemental analysis values are C48, 43%, H4,
05%, N3.99%, calculated values for Cl5HISNSOB, CA' (372,71) C 48.20%, H4,32%,
It was in good agreement with N3.75%.

In addition, when the mass spectrum was measured, a peak corresponding to CIl, a peak corresponding to m/e293, a peak corresponding to M-COCHz C1, m/e1
Each peak corresponding to 43 (100%) is shown.

Furthermore, the 'H-nuclear magnetic resonance vector is as shown as a specific example in the specification.

From the above results, it is clear that the isolated product is N-[2°-(5'-bromo)-thenylmethyl-
-Simethylanilide (hereinafter abbreviated as compound (1))
It became clear that. The yield is N~[2゛-(5
49.5% (3,04X 10-34o
le).

(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 I are listed in Table 1.

Furthermore, the general formula in Table 1 %formula% is the general formula [(] 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. ■Trademark] 1.5
A wettable powder was obtained by thoroughly pulverizing and mixing 1.5 parts by weight of the surfactant butadiene (surfactant) 60 (Lion Oil (Trademark)) and 87 parts by weight of Zikrite.

Formulation Example 2 Compound [34 parts by weight of A, 16 parts by weight of compound (17), 10 parts by weight of surfactant Tsurupol 5M100 (trademark of Toho Kagaku Kogyo ■), and 70 parts by weight of dimethylformamide were thoroughly mixed to obtain an emulsion.

Formulation example 3 Compound (A30.15 parts by weight, compound (39) 0.7
5 parts by weight, 3 parts by weight of dioctyl succinate, 3 parts by weight of sodium tripolyphosphate, 30 parts by weight of bentonite and 63.1 parts by weight of talc were thoroughly mixed and ground, water was added and kneaded, and then granulated and dried. Granules were obtained by sizing into medium size.

Formulation Example 4 40 parts by weight of bentonite, 56 parts by weight of talc, and 1 part by weight of 4 parts of sodium ligninsulfonylate are pulverized and mixed, water is added, kneaded, and granulated and dried to produce granules containing no active ingredient. Add 0.15 parts of compound (A) to 99.1 parts by weight of this granular material.
Granules were obtained by impregnating 0.75 parts by weight of compound (4o).

Example 1 A Wagner pot equivalent to 1/5000 are is filled with water-mixed paddy soil, and seeds of broad-leaved weeds such as Japanese grasshopper, Japanese grasshopper, firefly, and broad-leaved weeds such as Japanese grasshopper, Japanese azalea, and Japanese cypress are sown on the surface layer of the soil. Three rice seedlings (cultivar name: Akinishiki) at the 2.5-leaf stage (cultivar name: Akinishiki) in which the tubers were embedded were planted at a depth of 2 cm+. Thereafter, the rice was grown in a glass room at 20 to 25℃ under water conditions of about 3 ca+, and 7 days after transplanting the rice (when the wildflowers were at about 0.8 leaf stage) and 14 days after transplanting (when the wild grass was at about 2 leaf stage). ) to,
A wettable powder prepared according to Formulation Example 1 was diluted with water and sprayed in a predetermined amount. After that, they were grown in a glass room and treated with chemicals.
On the first day, 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 suppression rate (%) -; Normal 5: 100 (complete withering) ±: Slight damage 4 Near 5-9
9 +: Minor damage 3: 50-74
+: Medium damage 2: 25-49 1: 1-24 0:0<No effect observed at all)

[Brief explanation of the drawing]

FIG. 1 shows a 'H-NMR chart of Ni1f-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 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, halogen atoms, alkyl groups, or represents an alkoxy group, R_1_0 represents a hydrogen atom, an alkyl group, or an alkoxy group; R_1_1, R_1_2, and R_1_3 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxysulfonyloxy groups, alkylsulfonyloxy groups, or represents a carboxylic acid group or an ester thereof, Y represents an oxygen atom or an alkylene group,
Z represents a nitrogen atom or a methine group, and n represents 0 or 1. ) A herbicidal composition comprising a sulfonylurea derivative represented by the following as an active ingredient.