JPS61140502A - Herbicidal composition - Google Patents

Abstract

PURPOSE:The titled composition, having high safety for crops, exhibiting superior herbicidal effect essecially on direct-seeding cultivation of paddy-rice plant, capable of maintaining its effect for a long period, and containing an N- substituted-chloroacetanilide and a specific alicyclic amide derivative as active ingredients. CONSTITUTION:A herbicidal composition containing as active ingredients an N-substituted-chloroacetanilide expressed by formula I (R1, R2 and R3 represent H, halogen atom, alkyl, alkoxyl, etc.; R4 represents H or alkyl ; R5, R6 and R7 represent H, halogen atom, alkyl, alkenyl, etc.), which is a well-known superior herbicide but mostly a novel compound, and an alicyclic amide derivative expressed by formula II [R8 represents H, alkyl, alkoxyl, halogen atom, etc.; R9 and R10 represent H or alkyl; R11 represents formula III (R12 represents R9, R10 or halogen atom; R13 represents alkyl or halogen atom; X is halogen atom)], formula IV or V. EFFECT:The phytotoxicity to crops can be prevented or reduced even with a larger application amount than the single use of the compound expressed by formula I.

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 an alicyclic amide 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 developed the following general formula CI) R as an excellent herbicide that satisfies the above properties.

(However, in the formula, R represents a halogen atom, an alkoxy group, an alkylthio group, an alkoxyalkyl group, or an alkylthioalkyl group, and R3 and R8 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, represents an alkoxyalkyl group or an alkylthioalkyl group, R4 represents a hydrogen atom or an alkyl group,
R5, R, and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl ° groups, alkynyl groups,
We have already proposed an N-substituted chloroacetanilide represented by ( ) which represents an alkoxy group or an alkylthio group.
Patent Application No. 58-111077 and others).

Generally, when the purpose is weed control, it is fully expected that the larger the amount of herbicide used, the more completely the weeds will be killed over a long period of time. However, no matter how excellent a herbicide with low toxicity is, if it is used in an amount far exceeding the appropriate amount required for the above-mentioned purpose, there is a tendency for phytotoxicity to crops to occur. There are four possible causes of herbicidal selectivity between crops and weeds: ■ecological and morphological differences, ■differences in physiological functions, ■differences in absorption sites, and ■differences in growth stages. Under the harsh conditions of using pesticides at extremely high concentrations, there is a good possibility that they will cause phytotoxicity to crops.

The present inventors have discovered that the N-substituted-
In the use of chloroacetanilide as a herbicide,
We have been diligently conducting research on various herbicide compositions with the aim of using them more safely on crops.
A herbicide composition containing an N-substituted chloroacetanilide represented by the above general formula CI) and a specific alicyclic amide derivative as an active ingredient is extremely safe for crops while maintaining excellent herbicidal effects. 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), R + C0CI (IC1 CI) (wherein R, , R, and R3 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, represents an alkoxyalkyl group or an alkylthioalkyl group, R represents a hydrogen atom or an alkyl group, Rs, Rh and R represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups,
Indicates an alkoxy group or an alkylthio group. ) N-substituted-chloroacetanilide represented by the following general formula (II), CI[[], (IV) silR9 (wherein R1 is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a haloalkyl group) R9 and R111 are the same or different hydrogen atoms or the indicated groups [However, RIM represents a hydrogen atom, an alkyl group, or a halogen atom, Rt3 represents an alkyl group or a halogen atom, and
indicates a halogen atom. This is a herbicidal composition characterized by containing as an active ingredient an alicyclic amide derivative represented by the formula ().

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

(However, in the formula, R1, R1, 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, Ra and R? are the same or different hydrogen atoms,
A halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an alkylthio group. are bonded, R is a hydrogen atom or an alkyl group, Rt,
Compounds in which R3 and R4 are hydrogen atoms, Rs is an alkyl group, R6 is a hydrogen atom, an alkyl group, or an alkoxy group, and R7 is a hydrogen atom, an alkyl group, or a halogen atom are disclosed in US Pat. No. 3,901,917. It is publicly known. However, most of the others are new compounds.

In the general formula (1), Rt, Rz, Rs, Rs,
Specific examples of the halogen atom represented by R6 and R-I include chlorine, bromine, fluorine, and iodine atoms. Furthermore, in the general formula, R,, Rx, Ra, Ra,
The alkyl group represented by Rs, Ra, 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 1 to 6.
It is preferable that the number of Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 1s
o-propyl group, n-butyl group 1.1 so-butyl group,
Examples include t-butyl group, n-pentyl group, n-hexyl group, and the like. In the general formula CI), R1, Rx, R8, R
The alkoxy group represented by 2, Rh 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:
Examples include methoxy group, ethoxy group, n-propoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, and allyloxy group.

In the general formula (1), Rt, Rz, Rs, Rs,
The alkylthio group represented by R4 and R1 is not particularly limited and any known alkylthio group can be used, but generally has 1 carbon atom.
~6 linear or branched saturated or unsaturated groups are preferred. Specific examples of commonly used alkylthio groups include methylthio group, ethylthio group, n-propylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, and allylthio group.

Furthermore, in the general formula, the alkoxyalkyl groups represented by R, Rt and R5 are not particularly limited in the 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 allyloxye JP group, and the like. Furthermore, in the general formula, the alkylthioalkyl groups represented by Rt, Rz and R8 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 alkylthioalkyl group include methylthiomethyl group, methylthioethyl group, ethylthiomethyl group, n-propylthiomethyl group, t-butylthioethyl group, and allylthioethyl group.

Furthermore, in the above general formula, the alkenyl group represented by Rs, Ra, and Rt may be linear or branched, and the number of carbon atoms is not particularly limited. It is preferable that the number of Specific examples of the alkenyl group include a vinyl group, an allyl L 130-propenyl group, a 2-butenyl group, a 3-butenyl group, and the like. In addition, in the general formula, the alkynyl group represented by Rs, Rh, and Rv has 2 to 4 carbon atoms, regardless of whether it is linear or branched, and the number of carbon atoms is not particularly limited. It is preferable that Specific examples of the alkynyl group include ethynyl group, 2-propynyl group, and the like.

In the above N-substituted-chloroacetanilide, R3 is the same or different halogen atom, alkoxy group, alkylthio group, alkoxyalkyl group, or alkylthioalkyl group, and R- and R3 are the same or different hydrogen atom, halogen an atom, an alkyl group, an alkoxy group, an alkylthio group, an alkoxyalkyl group, or an alkylthioalkyl group, R4 is a hydrogen atom or an alkyl group,
R%, R, and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups,
Compounds that are an alkoxy group or an alkylthio group include 1.
Even when used at a low concentration of 5 g/a 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 has a high weeding effect of 50 g/a. 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=Rs is a substituent other than a hydrogen atom, this substituent is substituted at the ortho position of one CH- bonded to the thiophene ring, R4 is a hydrogen atom, and At least two of R1-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 the stronger above properties, so 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 near 3150-28001-1 and a characteristic absorption based on the carbonyl bond of the amide group near 1680-1660e1m-'. .

(b) Measure the mass spectrum (MS) and calculate the composition formula corresponding to each observed peak (generally expressed as m/e, which is the ion mass number m divided by the ion charge number e). By doing so, 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, when a sample subjected to measurement is expressed by the general formula (1), the molecular ion peak (hereinafter M(E
) is observed as an intensity ratio according to the isotope abundance ratio depending on the number of halogen atoms contained in the molecule, so it is possible to determine the molecular weight of the compound subjected to measurement.

Furthermore, for the N-substituted-chloroacetanilide represented by the general formula (1), MO-Crt, M(E)-cocotel, and R+ peaks are observed, allowing the bonding mode of the molecule to be known.

(c) By measuring lH-nuclear magnetic resonance spectrum ('H-NMR), N-
It is possible to know the bonding mode of hydrogen atoms present in substituted-chloroacetanilide. 'H-NMR (δ
, ppm: based on tetramethylsilane, in deuterated chloroform solvent).
The t-NMR diagram of N-chloroaceto-2,6-dimethylanilide (-thenylmethyl)-N-chloroaceto-2,6-dimethylanilide is shown in FIG. 1, and the analysis results are as follows.

That is, a singlet corresponding to 6 protons was observed at 2.0 ppm, and this can be attributed to the methyl group (d) substituted at the 2 and 6 positions of the phenyl group. 3.6
A singlet corresponding to two protons was observed in ppm,
This can be attributed to the methylene group (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). 2 protons at 6.67 ppm
A quartet corresponding to individual components was observed, and this can be attributed to the protons (a) and (b) substituted on the thiophene ring. 6.95-7.301) A multiplet corresponding to three protons was observed at pH, and this can be attributed to protons (e), (f), and (g) substituted with phenyl groups. 6 Represented by the general formula (I) above. To summarize the 'H-NMR characteristics of N-substituted-chloroacetanilide, the methylene proton of the chloroacetyl group is normally 3.6
~3.8 ppm When R4 is a hydrogen atom, the methylene proton of the aminomethylene group is a singlet of 4.7 ppm.
~5.0 pp+mpH (however, 2.0 pp+mpH on the aniline side)
If there is an asymmetric substituent at the 6-position, it may appear as a double line), and when R4 is an alkyl group, the methine proton of the aminomethine group is 5.7 to 6.
7ppmm, the protons on the thiophene ring side are 5.8 to 7
．． 4 ppm, and the protons on the benzene side are 6.0 to 7.7.
It tends to show a characteristic peak in 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.

Further, N-substituted-chloroacetanilide includes R, SR,, R,, R4, Rs, Rh, and R? in the general formula (1). Although its properties differ somewhat depending on the type, it is generally a pale yellow or yellow viscous liquid or solid at normal temperature and pressure, and many have extremely high boiling points.

``Specifically, as shown in the synthesis examples described later, the above compound tends to have a higher boiling point as its molecular weight increases, like general organic compounds.

The compound is soluble in common organic solvents such as benzene, ether, alcohol, chloroform, carbon tetrachloride, 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 (V), R.

(However, in the formula, RI-, Rt, 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. , R5, R, and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups) and an aniline derivative represented by the general formula CICH, CO
The N-substituted-chloroacetanilide represented by the general formula (1) can be obtained by reacting with chloroacetyl halide represented by

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

In the reaction between the compound represented by the general formula (V) and chloroacetyl halide, the molar ratio of both compounds may be appropriately determined as necessary, but it is usually the same molar ratio or a slightly 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 (V) 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. The hydrogen halide scavenger, which is preferred, 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, 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; acetonitrile, etc. N,N-dialkylamides such as nitrile 1iiN, N-dimethylformamide, N,N-diethylformamide;
Examples include dimethyl sulfoxide.

The order of addition of raw materials in the reaction is not particularly limited, but generally, the aniline derivative represented by the general formula (V) 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 10 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, that is, the N-substituted-chloroacetanilide represented by the general formula (f) above, from the reaction system is not particularly limited, and any known method may be employed.For example, the reaction solution may be cooled or allowed to cool naturally. After returning to room temperature or near room temperature and distilling off the reaction solvent and remaining hydrogen halide scavenger, 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 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 (I), the following method is also preferably employed.

General formula (where R+, Rt, 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) and X represents a halogen atom. , alkynyl 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 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 (V) with chloroacetyl halide as described above. Similar conditions can be adopted.

The above general formula [! ] The N-substituted chloroacetanilide represented by ] has a wide herbicidal spectrum against annual weeds such as field weeds, fireflies, and Japanese grasshoppers that occur in rice fields, as well as perennial weeds such as Omodaka, and does not cause chemical damage to paddy rice. It is an excellent herbicide that can effectively control herbicides.

The other component of the herbicidal composition of the present invention has the following general formula (I
f), (II) and (IV) R11(n) (However, in the formula, R8 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a haloalkyl group, and R9 and RID are the same or different hydrogen atoms or An alicyclic amide derivative represented by the following group [where RIg represents a hydrogen atom, an alkyl group or a halogen atom, RI3 represents an alkyl group or a halogen atom, and X represents a halogen atom] be.

In the above general formulas (n), (m) and (IV), R@s
R*, R+. , Rtg and RI3 are not particularly limited in terms of carbon number, and any alkyl 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-butyl group, 5ec-butyl group,
Examples include t-butyl group. In addition, the above general formula (n)
, (III) and (N), the alkoxy group represented by R1 is not particularly limited in its carbon number, and any group can be used, with those having 1 to 4 carbon atoms being particularly preferred. 0 Suitable alkoxy groups in the present invention include methoxy group, ethoxy group, n-propoxy group, l-propoxy group, n-butoxy group, l-butoxy group, 5ec
-butoxy group, t-butoxy group, etc.

In addition, the above general formulas (If), (III) and (fV
], examples of the haloalkyl group represented by R include those in which one or more of the hydrogen atoms of the alkyl group already mentioned are substituted with a halogen atom. As the alkyl group, the aforementioned alkyl groups can be used. Suitable haloalkyl groups in the present invention include fluoromethyl group, chloromethyl group, bromoethyl group, iodopropyl group, chlorobutyl group, difluoromethyl group, dichloroethyl group, dibromopropyl group, trifluoromethyl group, trichloromethyl group. group, tribromopropyl group, pentafluoroethyl group, and the like.

Furthermore, in the general formula ([3, (I[) and (IV)), R
a r R1! The halogen atoms represented by l Ra3 and X include fluorine, chlorine, bromine, and iodine atoms.

Among the alicyclic amide derivatives represented by the above general formulas (n), (III) and (IV), R8 is a hydrogen atom, R9 and R1° are a hydrogen atom or a methyl group, and R
Compounds in which Ig is a hydrogen atom, a methyl group, or a chlorine atom, R1 is a methyl group or a chlorine atom, and X is a chlorine atom are particularly preferably used.

Further, the alicyclic amide derivatives represented by the general formulas (II) and (III) are particularly effective in reducing drug damage and are therefore preferably used in the present invention.

As a method for producing the alicyclic amide derivatives represented by the above general formulas (II), (II) and (IV), known production methods can be employed without any limitations.

The herbicidal composition of the present invention comprises N-substituted-chloroacetanilide represented by the general formula (1) and the general formula (II
), (I[) and (IV) show excellent herbicidal effects and safety on crops in a wide range of usage ratios with alicyclic amide derivatives. However, the usage ratio of both is
Generally, the amount of the alicyclic amide derivative is in the range of 0.01 to 50 parts by weight per 1 part by weight of the N-substituted chloroacetanilide. More preferably, by adding 0.1 to 10 parts by weight of the alicyclic amide derivative to 1 part by weight of the N-substituted chloroacetanilide, safety for crops can be improved.

When the herbicide composition of the present invention is applied to paddy rice direct-seeding cultivation,
In particular, it is extremely safe for paddy rice. for example,
When the herbicide composition of the present invention is used for wild plants and rice seeds sown simultaneously in paddy soil, the germination of wild plants is completely inhibited when treated at a concentration of 0.1 g per 1 N-substituted chloroacetanilide. However, paddy rice costs 200
Even when treated with g, there is no effect at all. Therefore, generally 1
0.15-200 g per 7-l, preferably 0.5
It may be used in paddy fields in an amount of ~50g of active ingredient.

The herbicide composition of the present invention is effective even when treated before and after weed germination, is highly effective in soil treatment and foliage treatment, and is highly safe for crops. ing. 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 herbicide 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 other adjuvants as necessary, or it may be sprayed around crop seeds. It may also be applied as a covering.

The formulation form is not particularly limited, and conventionally known formulation forms can be used. For example, it can be used in the form of 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 preparation, any conventionally known solid carrier may be used without any restriction. Examples of solid carriers suitably used in the present invention include: It is 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, Inorganic substances such as apatite, zeolite, anhydrous silicic acid, 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, Synthetic or natural polymer compounds such as aldo resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal gum, and dammar gum; 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. The following are examples of liquid carriers preferably used in the present invention. 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, diptyl 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, or 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, fluidity 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 obtained by polymerizing and adding ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Products obtained by polymerizing and adding 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. Addition of stearyl phosphate,
Products obtained by polymerizing and adding ethylene oxide to mono- or dialkyl phosphoric acids such as dilauryl phosphoric acid; products obtained by polymerizing and adding ethylene oxide to amines such as dodecylamine and stearic acid amide; higher fatty acid esters of polyhydric alcohols such as sorbitan, and ethylene oxide to them. Ethylene oxide and propylene oxide were polymerized and added. Examples include 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 sulfones such as sodium sulfosuccinate dioctyl ester and sodium 2-ethyl/rehexene sulfonate. Acid salts; aryl sulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, 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 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, 1 part by weight of an alicyclic amide derivative and 5 parts by weight of N-substituted chloroacetanilide are dissolved in an organic solvent, a surfactant and a carrier are added to the solution, and the mixture is thoroughly ground. There is a method of obtaining a wettable powder by removing the organic solvent after mixing.

For example, as a specific method for preparing an emulsion, 10 parts by weight of an alicyclic amide 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. There is a method to obtain an emulsion.

Furthermore, for example, as a specific method for preparing granules, 1 part by weight of an alicyclic amide 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 has high safety against crops, and is characterized by high safety against rice, especially when applied in flooded fields. Among these, it is particularly effective when applied to direct-seeded paddy rice cultivation.

Therefore, even if the application amount is higher than when N-substituted-chloroacetanilide is used alone, phytotoxicity to crops can be prevented or reduced.

As a result, the herbicide composition of the present invention can completely kill weeds that could not be completely killed by applying a small amount of N-substituted chloroacetanilide alone by increasing the amount applied. It is possible to maintain the herbicidal effect over a long period of time. Moreover, it has the characteristic that chemical damage to crops can be prevented.

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.

Incorporation of N-1-chloroacetanilide (Synthesis Example 1) N-(2'-(5'-bromo)-chenylmethyl)-2
, 6-dimethylaniline 1.81 g (6,14X
1 (I'mole) benzene 40 copper! 0.81 g of triethylamine (7,98x 10-'
mole) and placed in ice water. Then 0.83 g of chloroacetyl chloride (7,37x 10-3
A benzene solution (15+wf) of mol) was slowly 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 yal of water, 2N
- Hydrochloric acid 50n+1 followed by 50mj of water! The benzene layer was dried with anhydrous sodium sulfate.

After that, it was purified by column chromatography, and 1.13g of yellow solid was obtained.
I got it. As a result of measuring the infrared absorption spectrum of this product, it showed an absorption based on the C-H bond at 3110 to 2900 cm-' and a strong absorption based on the carbonyl bond of the amide group at 1670 cm+-1. Its elemental analysis value is C48.4
3%, 84.05%, N3.99%, C+sH
Calculated values for +5NSOBrCll (372,71): C 48.20%, H4,32%, N3.75%
There was good agreement.

In addition, when mass spectra were measured, Il/e37
1 is the molecular ion peak (MO) corresponding to the molecular weight, m/
Peak corresponding to MO-C1 at e336, m/e293
peak corresponding to MO-COCHt C1l, m/e
Each peak corresponding to 143 (100%) is shown.

Furthermore, the IH-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-chloroacet-2,
It became clear that it was 6-dimethylanilide (hereinafter abbreviated as compound (1)).

The yield was 49.5% (3
,04×10-'mole).

(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 is the general formula (1) above. R.

s 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-chloroacetanilides are indicated by compound numbers [(1) to (66)] in the synthesis side.
), and alicyclic amide derivatives are represented by the following symbol ([A]
~ [Z]).

Formulation example 1 Compound [12 parts by weight of A, 10 parts by weight of compound (3), surfactant Tsurupol 800A (Toho Chemical Industry @ Tsuji trademark)
A wettable powder was obtained by thoroughly pulverizing and mixing 1.5 parts by weight of the surfactant Detardient 60 (Lion Oil ■ Trademark), 1 part by weight of 1.5 parts by weight, and 85 parts by weight of Zikrite.

Formulation example 2 Compound CB) 10 parts by weight, compound (3) 5 parts by weight, surfactant Tsurupol 5M100 (Toho Chemical Industry Trademark)
15 parts by weight and 70 parts by weight of xylene were thoroughly mixed to obtain an emulsion.

Formulation Example 3 Compound [I] 1 part by weight, Compound (39) 1 part by weight,
4 parts by weight of dioctyl succinate, 4 parts by weight of sodium tribophosphate, 41 parts by weight of bentonite and 49 parts by weight of talc were thoroughly mixed and pulverized, water was added, kneaded, granulated and dried, and sized into 14 to 32 meshes. Granules were obtained.

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 field grass, Japanese cypress, bulrush and other broad-leaved weeds such as Japanese grasshopper, Japanese cypress, and Japanese cypress were sown on the surface layer of the soil. I embedded tubers of Cyperus japonica. Furthermore, after sowing 100 rice seeds (cultivar name: calrose) on the soil surface, they were grown in a glass room at 20 to 25°C under warm water conditions of approximately 3 cm +. At the same time, the wettable powder prepared according to Formulation Example 1 was diluted with water and a predetermined amount was dropped. 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.

Weeding effect Weed suppression rate (%) 5:100 (Complete death) 4nia 5-99 3:50-74 2225-49 1: 1-24 0:O<no effect at all) Regarding paddy rice phytotoxicity The ratio of the normally grown paddy rice grains to the untreated plot was calculated and expressed on a 5-level scale from - to +++.

Paddy rice chemical damage (%) 1: Normal (0) ±: Very small diameter (1-10) 12 Minor damage (11-29) 12 Medium damage (30-69) 10/10: Major damage (70- 100) Example 2 In the same manner as in Example 1, various herbicide compositions were
Table 3 shows the results of investigating the chemical damage caused to paddy rice.

The criteria for paddy rice phytotoxicity in Table 3 are the same as in Example 1.

Table 3

[Brief explanation of the drawing]

FIG. 1 shows an IH-NMR chart of N-substituted-chloroacetanilide obtained in Synthesis Example 1. Patent Applicant: Tokuyama Soda Co., Ltd. Procedural Amendment December 1980 Japan Patent Office Commissioner Manabu Shiga Patent Application (3) 26 Title of Invention Herbicide Composition 3, filed on December 14, 1980 Relationship with the case of the person making the amendment Patent applicant address: 1-1-4, Mikage-cho, Tokuyama-shi, Yamaguchi Prefecture, date of fi-authorial order: 5, subject of amendment: Column 1 of Detailed Description of the Invention of R of Meijis 6. Details of amendment (1) On page 12, line 5 of the specification, "allyloxyel group" is amended to "allyloxyethyl group." (2) From page 50 of the memorandum

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 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R_8 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a haloalkyl group, and R_9
and R_1_0 represent the same or different types of hydrogen atoms or alkyl groups, and R_1_1 is a group represented by ▲There are mathematical formulas, chemical formulas, tables, etc. [However, R_1_2 represents a hydrogen atom, an alkyl group, or a halogen atom, and R_1_3 represents an alkyl represents a group or a halogen atom, and X represents a halogen atom. ]. ) A herbicidal composition comprising an alicyclic amide derivative represented by the following as an active ingredient.