JPS60202803A - Herbicide composition - Google Patents

Abstract

PURPOSE:A herbicide composition having a wide herbicidal spectrum with a small amount of it, having high safety to crops, comprising an N-substituted chloroacetanilide and a pyrazole derivative as active ingredients. CONSTITUTION:A herbicide composition comprising (A) a compound shown by the formula (A is H, halogen, alkyl, alkoxy, or alkylthio; R1-R3 are as shown for A) having a wide herbicidal spectrum not only on annual weeds such as Echinochloa crus-galli Beauv. var. particola Ohwi., monochoria, etc. occurring in paddy fields but also on perennial weeds such as bulrush, water nutgrass, etc., and (B) a compound shown by the formula II [R4 and R5 are alkyl; Y is halogen, or NO2; n is 1, or 2; Z is alkyl, phenyl, phenacyl, group shown by the formula III (Z' is H, or halogen), etc.] showing excellent effect on broad-leaved weeds including perennial weeds but low effect on weeds such as Echinochloa crus-galli Beauv. var. praticola Ohwi., water nutgrass, etc. in a weight ratio of the component A to B of 1:0.2-20 as active ingredients.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a herbicidal composition characterized by containing an N-substituted monoaloacetanilide and a pyrazole derivative as active ingredients.

As a property essentially required for herbicides, τ'rXlr
1A/11r1'Ik11omi 1-hZ→---Fumi day n→
Heat--1bf-b'' Tol^ = being safe for things;
Two, it has a broad herbicidal spectrum necessary to completely kill the many types of fine grass growing in crop-growing areas, and three, the herbicide's efficacy lasts for a long time.
It has a more effective herbicidal effect when applied in small amounts.
It is.

The present inventors have conducted extensive research with the aim of developing an excellent herbicide that satisfies the above-mentioned properties, and have obtained the following general formula El) R (however, the person in the formula is...a rodan atom, an alkoxy group, or an alkylthio group, and R1゜R2 and R5 each represent the same or different water molecules, halogen atom -F, alkyl group, alkoxy group, or alkylthio group). (%Gan Sho 58-111077). The inventor further
The herbicidal composition containing the N-substituted-chloroacetanilide represented by the above general formula [1] and the pyrazole derivative as active ingredients exhibits a synergistic effect that cannot be expected from their individual properties, that is, a low It was discovered that it has a wide herbicidal spectrum depending on the dosage.

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

That is, the present invention provides the following general formula CI) R chant (However, the person in the formula is a hydrogen atom or a halogen atom.

It represents an alkyl group, an alkoxy group, or an alkylthio group, and R1, R2, and R5 are the same or different hydrogen atoms, . . . rogene atom.

Indicates an alkyl group, an alkoxy group, and an alkylthio group. )
N-substituted-chloroacetanilide represented by the following general formula [11] (wherein R4 and R5 are an alkyl group, Y is) a \rogen atom or a nitro group, and n is 1 or 2. Z is an alkyl group; an acetylalkyl group; a substituted or unsubstituted phenyl group, a benzyl group, a phenacyl hydrogen atom or a norogen atom). ) as an active ingredient.

One component of the herbicidal composition of the present invention has the following general formula C
It is an N-substituted chloroacetanilide represented by 1).

(However, the person in the formula is a hydrogen atom, -, rogen atom.

It represents an alkyl group, an alkoxy group, or an alkylthio group, and R1*R2 and R5 are the same or different hydrogen atoms, . . . rogene atom.

Indicates an alkyl group, an alkoxy group, and an alkylthio group. ) Among the N-substituted chloroacetanilides represented by the above general formula [I], A is an alkyl group before a hydrogen atom, and R
Compounds in which 1 is an alkyl group, R2 is a hydrogen atom, an alkyl group, or an alkoxy group, and R is a hydrogen atom, an alkyl group, or a halogen atom are disclosed in US Pat. No. 59
No. 01917. However, most of the others are new compounds.

In the above general formula, A+R1*Rz and R5 are represented by...Specific examples of the rogen atom include chlorine, bromine, fluorine, and iodine atoms. In the general formula CI),
The alkoxy groups represented by A, R1 #R2 and R3 are not particularly limited, but are generally preferably linear or branched saturated or unsaturated groups having 1 to 6 carbon atoms. A specific example of the alkoxy group that is generally preferably used is an ethoxy group.

Ethoxy group, n-propoxy group, t-butoxy group, n-
Pentoxy group, n-hexoxy group.

Examples include allyloxy group.

In the general formula [11], the alkylthio groups represented by A, R1, R2, and R5 are not particularly limited and any known alkylthio groups can be used, but they are generally linear or branched alkylthio groups having 1 to 6 carbon atoms. Saturated or unsaturated groups are preferred. Specific examples of the alkylthio group suitably used include methylthio group, ethylthio group, n-propylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, and allylthio group. Furthermore, the general formula [
)), the alkyl groups represented by A, R1, R2, and R3 are not particularly limited and any known alkyl group can be used, but generally a linear or branched saturated group having 1 to 6 carbon atoms. Alternatively, unsaturated groups are preferred. Specific examples of the alkyl group that are generally preferably used include methyl group, ethyl group, n-propyl group, and 1θ0-propyl group.

n-butyl group, 1so-butyl group, t-butyl Men
-pentylJln-hexyl group, allyl group, ethynyl group and the like.

The structure of the N-substituted-chloroacetanilide represented by the general formula [1] can be confirmed by the following means.

(b) By measuring the infrared absorption spectrum (IR), we observed an absorption based on the CH bond in the vicinity of 5150 to 2800 α-1 and a characteristic absorption based on the carbonyl bond of the amide group in the vicinity of 1680 to 1670 Iff. I can do it.

(b) Measure the mass spectrum (m days) and find the composition formula corresponding to each peak observed (-the membrane pressure is the value expressed as m / e, which is the ion mass number m divided by the ion charge number e). When calculated, the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule can be known from K. That is, when a sample subjected to measurement is expressed by the general formula El) 1 , the molecular ion peak (hereinafter M(9
) is observed at an intensity ratio according to the isotope abundance ratio depending on the number of no-rogen atoms contained in the molecule, so it is possible to determine the molecular weight of the compound subjected to measurement. Furthermore, regarding the N-substituted-chloroacetanilide represented by the general formula [l], M"-CL, MΦ-C
Characteristic strong peaks corresponding to OC'H2CA and AfuCH269 were observed, and the binding mode of the molecules could be known.

(c) 1H-nuclear magnetic resonance spectrum ('H-NMR)
By measuring K, it is possible to know the bonding mode of the hydrogen atoms present in the N-substituted-chloroacetanilide represented by the general formula [I]. H-NMR of N-substituted-chloroacetanilide represented by the general formula [l] (
a, ppm: tetramethylsilane standard (in double chloroform solvent) as a specific example of N-[2'-(5'-bromo)-chenylmethyl)-N-chloroaceto-2,6-
Figure 1 shows the 'H-NMR diagram of dimethylanilide. The analysis results are as follows.

(h) That is, a singlet corresponding to 6 protons IfC is observed at 2.0 ppm, and can be attributed to the methyl group (d) substituted at the 2 and 6 positions of the phenyl group. 3.6p
A singlet corresponding to two protons was observed at pm, which can be attributed to the methylene group (b) in the chloroacetyl group. A singlet corresponding to two protons was observed at 4.75 ppm, and can be attributed to the methylene group (C). A quartet corresponding to two protons was observed at 6.67 ppm, indicating a proton member substituted with thiophene@VC.

It can be attributed to (b). 6.95-7.60p
A multiplet corresponding to 3 protons was observed in pm, and the protons (e), (f), substituted with phenyl groups were observed.
It can be attributed to (g).

Summarizing the 'H-NMR characteristics of the N-substituted-chloroacetanilide represented by the above general formula [I], the methylene proton of the chloroacetyl group is usually 3.6 to 6.8
ppm, and the methylene proton of the aminomethylene group is a singlet near 4.8 ppm (however, if there is an asymmetric busy substituent at position 2.6 on the aniline side, it becomes a double line). ), protons on the thiophene ring side tend to show characteristic peaks at 5.8 to 7.4 ppm K, and protons on the benzene side tend to show characteristic peaks at 6.0 to 7.7 ppm.

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

The properties of -N-substituted-chloroacetanilide vary depending on the types of A, R1*R2, and R3 in the general formula [I], but in general, it is a pale yellow or yellow viscous liquid or a yellow viscous liquid at room temperature and normal pressure. Many of them are solids and have extremely high boiling points. More specifically, as shown in the synthesis examples described later, the boiling point of the above compound tends to increase as the molecular weight increases, like general organic compounds. The compound is soluble in common organic solvents such as benzene, ether, alcohol, chloroform, carbon tetramide, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide, but almost insoluble in water.

The method for producing the N-substituted chloroacetanilide represented by the general formula [I] is not particularly limited. A typical manufacturing method is described below.

General formula (where A is a hydrogen atom), represents a rogen atom, an alkyl group, an alkoxy group, or an alkylthio group, R1,
R2 and R5 are the same or different hydrogen atoms, respectively.
- Indicates a rogen atom, alkyl group, alkoxy group, and alkylthio group. ) and the compound represented by the general formula CtCH
2COx (where X) represents a ninerogen atom. ) by reacting with chloroacetylnologenide represented by
Chloroacetanilide can be obtained.

The aniline derivative represented by the general formula [nI] as a raw material can be obtained by any method.

In the reaction between the compound represented by the above general formula [■] and chloroacetylno-10genide, 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 slightly smaller amount of chloroacetylno-10genide. It is common to use a molar excess.

Further, in the above reaction, hydrogen halide is produced as a by-product.

This hydrogen halogenide reacts with the compound represented by the general formula [1] in the reaction system, causing a decrease in the yield of the product, so usually a hydrogen halogen scavenger is added to the reaction system. It is preferable that they coexist. The hydrogen halogenide scavenger is not particularly limited, and any known one can be used. Generally preferred scavengers include trialkylamines such as trimethylamine, triethylamine, tripropylamine, pyridine, sodium alcoholade,
Examples include sodium carbonate.

It is generally preferable to use an organic solvent in the reaction. Examples of solvents that are preferably used include:
benzene, toluene.

Aliphatic or aromatic hydrocarbons such as xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, ethylene chloride, or halogenated hydrocarbons; ethers such as diethyl ether, dioxane, tetrahydrofuran; acetone, methyl ethyl ketone, etc. Ketones; Nitriles such as acetonitrile: N such as N,N-dimethylformamide, N,N-diethylformamide, etc.
, N-dialkylamides; dimethyl sulfoxide and the like.

The order of addition of the raw materials in the reaction is not particularly limited, but generally, the compound represented by the general formula [■] is dissolved in a solvent, charged into a reactor, and the chloroacetyl halide dissolved in the solvent is added under stirring. That's what you should do. Of course, it is also possible to continuously add the nine raw materials to the reaction system and to continuously take out the produced reactants from the reaction system.

The temperature in the reaction can be selected from a wide range, generally #'1-20C to 150C, preferably 00 to 120C.
It is sufficient to choose from the range. The reaction time varies depending on the type of raw material, but is usually 5 minutes to 10 days, preferably 1
It is sufficient to select from the range of ~40 hours. It is also preferable to stir during the reaction.

The method for isolating and purifying the desired product, ie, the N-substituted-chloroacetanilide represented by the general formula [I], 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 remaining hydrogen 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 halogenide and the hydrogen halogenide 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 isolation and purification by vacuum distillation, purification by chromatography,
If the product is a solid, certain h can also be purified by recrystallization from a solvent such as hexane.

Furthermore, the general formula % formula % (where A is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkoxy group or an alkylthio group, and X is).
Indicates a rogen atom. ) and a 2-substituted thiophene represented by the general formula (where Rj, R2 and R5 are the same or different hydrogen atoms, . . . rogene atom, alkyl group.

Indicates an alkoxy group or an alkylthio group. ) The N-substituted-chloroacetanilide represented by the general formula CI') can also be obtained by reacting with chloroacetanilide represented by the formula CI').

The 2-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 compound represented by the general formula CI[I] with chloroacetyl halide and the separation and purification method described above. Similar conditions can be adopted.

The N-substituted-chloroacetanilide represented by the above general formula [I] is a novex that occurs in rice fields.

It has a wide spectrum of herbicidal properties against annual weeds such as Japanese grasshopper, as well as perennial weeds such as firefly, Japanese cypress, Omodaka, and Urikawa, and causes chemical damage to paddy rice.6
(It is an excellent herbicide that can effectively control the herbicide. It is especially effective against the perennial water pyre, which has become a problem in recent years.)
When sprayed in small amounts, it has an outstanding herbicidal activity unparalleled by other herbicides.

Other components of the herbicidal composition of the present invention are represented by the following general formula (11 (where -Ra, Rs are alkyl groups, Y is a halogen atom or a nitro group, nFil or 2. Z is an alkyl group; an acetylalkyl group; a substituted (C) is an unsubstituted phenyl group, benzyl group, phenacyl hydrogen atom or halogen atom).
This is a herbicidal composition characterized by containing a pyrazole derivative represented by the following as an active ingredient.

Examples of the alkyl groups represented by R4, R5 and 2 in the above general formula [1] include methyl group, ethyl group, n-propyl group, and 1-propyl group. Among these, those having a methyl group are preferably used because they have high herbicidal activity. Specific examples of the halogen atoms represented by Y and 2' in the general formula El) include chlorine, bromine, and fluorine.

Each atom of iodine is mentioned. In particular, Y is chlorine, n is 2
Pyrazole derivatives in which chlorine is bonded to the 2- and 4-positions of the benzene ring have particularly high herbicidal activity and are preferably used. Furthermore, the acetylalkyl group represented by 2 in the above general formula [11] is an acetylmethyl group.

Examples include acetylethyl groups and the like.

Furthermore, the substituents for the phenyl group, benzyl group, and phenacyl group represented by 2 in the above general formula [11] include:
Examples include halogen atoms such as chlorine, bromine, fluorine, and iodine, methyl groups, ethyl groups, alkyl groups, and nitro groups. Those substituted with one or two of these substituents are usually used.

As a method for producing the pyrazole derivative represented by the above general formula [11], any known production method may be used without limitation.

The pyrazole derivative represented by the general formula CI) is known to induce chlorosis by photooxidation of chlorophyll based on the inhibition of carotenoid biosynthesis, and is highly effective against broad-leaved weeds including perennial weeds. However, it has a property that its effect is weak on weeds such as wild grass, azalea, and Japanese cypress.

The herbicidal composition of the present invention comprises an N-substituted-chloroacetanilide represented by the general formula CI) and the general formula [11
Excellent herbicidal effects can be obtained in a wide range of usage ratios with the pyrazole derivatives shown in 3. However, the ratio of the pyrazole derivative to 1 part by weight of y-fl-chloroacetanilide is generally in the range of 0.01 to 50 parts by weight. Furthermore, preferably, the herbicidal effect becomes more excellent by using 0.2 to 20 parts by weight of the pyrazole derivative 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 at the same time in paddy soil, 0.1 per are
When treated with a concentration of t, the germination of wild grass is completely inhibited, but paddy rice is treated with a concentration of 100% and has no effect even when treated with 9%.

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

The herbicide composition of the present invention is effective even when treated before and after weed germination, and is also highly effective in soil treatment and foliage treatment.

Application sites include paddy fields, fields of various grains, legumes, cotton, vegetable crops, orchards, lawns, pastures, etc.
Tea gardens, mulberry gardens, forest areas.

It is useful in a wide range of non-agricultural areas.

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, powder.

It can be prepared and used as a coarse powder, a single fine granule, a wettable powder, an emulsion, a flowable preparation, an oil suspension, 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, etc.: talc, mica monophyllite, pumice, bursa culite, gypsum, calcium carbonate, dolomite, porphyry earth, magnesium lime.

Inorganic substances such as apatite, zeolite, anhydrous silicic acid 9 synthetic calcium silicate; soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch.

Vegetable organic substances such as crystalline cellulose; coumaron resin 2 synthetic or natural polymer compounds such as petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum 8 copal gum, tanmal gum;
Examples include 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; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene; carbon tetrachloride, chloroform, trichloroethylene, monochlorobenzene, Chlorinated hydrocarbons such as 0-chlorotoluene; ethers such as dioxane and tetrahydrofuran; acetone and methyl ethyl ketone.

Ketones such as diimbutylketone, cyclohexanone, acetophenone, inholone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methacool, n-hexanol, ethylene Alcohols such as glycol and diethylene glycol: ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether; polar solvents such as dimethylformamide, dimethyl sulfoxide, and water.

In addition, the preparation of the formulation in the present invention includes emulsification, dispersion, wetting, spreading, binding, and disintegration adjustment.

Conventionally known surfactants can be used without any restriction for the purpose of stabilizing active ingredients, improving fluidity, preventing rust, etc. As a surfactant, it is nonionic.

Cationic, anionic and zwitterionic types are used, but usually non-ionic and/or anionic types are used.

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; and those obtained by polymerizing and adding ethylene oxide to alkylphenols such as inoctylphenol-unonylphenol. Book: Polymerized addition of ethylene oxide to alkylnaphthol such as butylnaphthol and octylnaphthol; Polymerized addition of ethylene oxide to higher fatty acids such as valmitic acid, stearic acid, and oleic acid; Stearyl phosphoric acid, dilauryl phosphoric acid, etc. Polymerization and addition of ethylene oxide to mono- or dialkyl phosphoric acid of Examples include esters of polyhydric fatty acids and alcohols such as nidioctyl succinate, which is obtained by polymerizing and adding ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, alkyl sulfate ester salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt; alkyl sulfones such as sodium sulfonic acid dioctyl ester and sodium 2-ethylhexene sulfonate. Acid salts: Improvil sodium naphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate.

Examples include arylsulfonates such as sodium dodecylbenzenesulfonate; phosphates such as sodium tripolyphosphate.

Furthermore, in the formulation of the present invention, conventionally known adjuvants may be used without any restriction. 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 1llff 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, 10 parts by weight of a pyrazole derivative and 1 part by weight of N-f%-chloroacetanilide were dissolved in an organic solvent, and a surfactant and a carrier were added to the solution and thoroughly ground and mixed. There is a method of obtaining a wettable powder by subsequently removing the organic solvent.

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

Furthermore, for example, as a specific method for preparing granules, 10 parts by weight of a pyrazole derivative.

1 part by weight of N-f-chloroacetanilide.

There is a method of obtaining granules by thoroughly mixing a surfactant and water, then adding a carrier and a surfactant, stirring, extruding to a predetermined particle size, and drying.

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, it has a wide herbicidal spectrum. 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.

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-substituted-chloroacetanilide (Synthesis Example 1) N -C2'-(5'-bromo)-chenylmethyl]-
2,6-dimethylaniline 1.81 ? (6-14X
Dissolve benzene ysoTnt<0.8 it (7,98Xl 0'
-3 mole) and placed in ice water. Then chloroacetyl chloride 0.85tC7,57X 10-
5 mole) of benzene solution (15 mj) was gradually added. After stirring for 3 hours, the mixture was heated at 50C for 1 hour. After cooling the reaction mixture to room temperature, 50 ml of water, 2
The benzene layer was washed with 50 tIlt of N-hydrochloric acid and then 50+ nt of water, and the benzene layer was dried over anhydrous sulfuric acid. After that, it was purified by column chromatography and a yellow solid 1.
I got 162. As a result of measuring the infrared spectrum of this product, it showed an absorption based on the c-H bond at 3110 to 2900 crn-', and a strong absorption based on the carbonyl bond of the amide group at 1670tYn'.

Its elemental analysis value is 048.45%, H4.05%.

N 5.99%, C15H15NSOBrCt
The calculated value for (372,71) is 048.20
%, H4, 32%, N! It was in good agreement with 1.75%.

Also, when we measured the mass spectrum, m/e371
The molecular ion peak corresponding to the molecular weight, M”, m/e3
The peak corresponding to M”-CL at 56 + m/e 2
93, the peak corresponding to MΦ-COCH2ct, m/e
Each peak corresponding to 143 (100%) Ic BMCH2° is shown.

Furthermore, the 1H-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 N-[2'-(5'-bromo)-thenylmethyl]-N-chloroaceto-2,6
-Simethylanilide (hereinafter abbreviated as compound (1))
It became clear that. The yield is N-(2'-(5
'-bromo)-thenylmethyl]-2,6-cymey-
49.5% (5,04X 10-3
mole).

(Synthesis Example 2) Properties and physical properties of N-substituted-chloroacetanilide synthesized in the same manner as Synthesis Example 1 (1 point).

The characteristic absorption values in the infrared absorption spectrum and the elemental analysis results are also summarized in Table 1.

General formulas in Table 1 ) is the general formula [11 1 Good luck means.

ct Next, formulations and examples of the herbicide composition of the present invention will be shown. In addition, in the compounding agents and examples, N-substituted-chloroacetanilide is the number of the compound in the synthesis side (1) to (52))
The pyrazole derivatives are represented by the following symbols ([A] to [
O]).

Formulation example 1 10 parts by weight of compound [A], 4 parts by weight of compound (1), surfactant Nluball 800A [Toho Chemical Industry @) trademark]
1.5 parts by weight, 1.5 parts by weight of surfactant Detargent 60 [Lion Oil @) trademark] and Zikrite 86
Parts by weight were ground and mixed to obtain a wettable powder.

Formulation example 2 Compound CA) 10 parts by weight, compound (10) 5 parts by weight, surfactant Nlupol 5M1001: Toho Chemical Industry (
315 parts by weight of the Co., Ltd. trademark and 70 parts by weight of xylene were thoroughly mixed to obtain an emulsion.

Formulation Example 3 Compound [37 parts by weight of A, 1.0 parts by weight of compound (20), 4.0 parts by weight of dioctyl succinate.

Tripolyphosphate 4.0 parts by weight, bentonite 42
Parts by weight and 42 parts by weight of talc were thoroughly mixed and pulverized, water was added and kneaded, granulated and dried, and the particles were sized to 14 to 32 mesh to obtain granules.

Formulation Example 4 40 parts by weight of bentonite, 5.5 parts by weight of talc, and 5 parts by weight of sodium tripolyphosphate are pulverized and mixed, added with water, mixed, and then granulated and dried to produce granules containing no active ingredient. 7 parts by weight of compound [A] and 8 parts by weight of compound (50) were impregnated into 85 parts by weight of the granules to obtain granules.

Example 1 A Wagner bot equivalent to 1/5000 are is filled with water-mixed paddy soil, and seeds of broad-leaved M grasses such as Japanese field grass, Japanese cypress, bulrush, and other broad-leaved grasses such as Japanese grass, Japanese azalea, and Japanese cypress are sown on the surface layer of the soil. Embedded tubers of Cyperus japonica. In addition, three rice seedlings (variety name: Akinishiki) at the Vc2.5 leaf stage were planted at a depth of two. after that,
The rice was grown in a glass room at 20 to 25°C under submerged water conditions, and 7 days after transplanting the rice (when the wildflowers were at about 0.8 leaf stage) and 14 days later (when the wild grass was at about 2 leaf stage). , Formulation example 1
A wettable powder prepared according to the method was diluted with water and a predetermined amount was added dropwise. Thereafter, they were grown in a glass room, and on the 21st day after the chemical treatment, the herbicidal effect and the chemical damage caused to paddy rice were investigated. The results are shown in Table 2.

Herbicidal effect: Paddy rice chemical damage Weed suppression rate (%) -: Normal 5:100 (complete withering) ±: Slight damage 4 Near 5-99 +: Minor damage 3:50-74 +: Medium damage 2: 25-49 1: 1-24 0:0 (no effect observed at all)

[Brief explanation of drawings]

FIG. 1 shows a chart of 1H-nuclear magnetic resonance spectrum of N-substituted-chloroacetanilide obtained in Synthesis Example 1. Patent applicant: Tokuyama Soda Co., Ltd.

Claims (1)

[Scope of Claims] A rogen atom of the following formula (wherein A is a hydrogen atom). It represents an alkyl group, an alkoxy group, or an alkylthio group, and R1#, R2, and R5 each represent the same or different hydrogen atom, . . . rogene atom, an alkyl group, an alkoxy group, or an alkylthio group. ) and an N-substituted monochloroacetanilide represented by the following formula (where R4 and R5 are an alkyl group, Y is a halogen atom or a nitro group, n is 1 or 2, Z is an alkyl group; an acetylalkyl group; a substituted or (substituted phenyl group, benzyl group, phenacyl atom or halogen atom). ) A herbicidal composition comprising a pyrazole derivative represented by the following as an active ingredient.