JPS61130202A - Herbicidal composition - Google Patents

Abstract

PURPOSE:A herbicidal composition that contains, as active ingredients, an N- substituted-chloroacetanilide and a diphenyl ether derivative, thus developing synergetic effect to show a wide range of herbicidal spectrum with a low dose. CONSTITUTION:The objective composition is prepared by using (A) a compound of formula I (R1-R3 are H, halogen, alkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl; R4 is H, alkyl; R5-R7 are H, halogen, alkyl, alkenyl, alkinyl, alkoxy, alkylthio) such as N-[2'-(5'-bromo)-thienylmethyl]-N-chloroaceto-2,6- dimethylanilide and (B) another compound of formula II (R8-R12 are H, halogen, NO2, alkyl, alkoxy, alkylsulfinyl, alkoxycarbonyl, carboxyl or its base) at a weight A/B ratio of 1/(0.01-50), preferably 1/(1-20).

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 diphenyl ether 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 carried out the following general formula (1): group, alkoxyalkyl group, or alkylthioalkyl group, R2 and R8 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups, and R4 is a hydrogen atom or represents an alkyl group, Rs, 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. ) have already been proposed (Japanese Patent Application No. 58-111077 and others). The present inventors further provided that the N-substituted-
A herbicide composition containing chloroacetanilide and a specific diphenyl ether derivative as active ingredients exhibits a synergistic effect that could not be expected from their individual properties;
In other words, it has been 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 (1), (wherein R+, R2, and R3 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups. , R4 represents a hydrogen atom or an alkyl group, R5, R.

and R1 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups. ) with N-substituted-chloroacetanilide (wherein Rs, Rq
, R+R8, R, □ and RI3 are the same or different hydrogen atoms, halogen atoms, nitro groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, alkylsulfinyl groups, alkoxycarbonyl groups or carboxyl groups or its base. ) as an active ingredient.

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

(However, in the formula, R1, 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. , 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-chloro represented by the above general formula (1) A small proportion of acetanilide compounds, that is, the 2-position of the thiophene ring and -CH- are bonded, R9 is a hydrogen atom or an alkyl group, R2, R:l and R4 are hydrogen atoms, and R9 is an alkyl group, R8 is a hydrogen atom, an alkyl group or an alkoxy group, R7 is a hydrogen atom,
Compounds which are alkyl groups or halogen atoms are known from US Pat. No. 3,901,917. However, most of the others are new compounds.

In the general formula (I), R+, Rz, R3, Rs, R
Specific examples of the halogen atoms represented by h and R7 are:
Examples include chlorine, bromine, fluorine, and iodine atoms. In addition, in the general formula, R,, R,, R3, R4, Rs,
The alkyl group represented by Rh and R7 may be linear or branched, and the number of carbon atoms is not particularly limited.

However, from the viewpoint of ease of handling raw materials, it is preferable that the number of carbon atoms is 1 to 6. Specific examples of the alkyl group include methyl group, ethyl group, Ω-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 (r), R1, R2, R), Rs, R
The alkoxy group represented by 6 and R7 is not particularly limited, but a linear or branched saturated or unsaturated group having 1 to 6 carbon atoms is generally preferred. Specific examples of the alkoxy group that are generally preferably used include methoxy group, ethoxy group, n-propoxy group, L-butoxy group, n-pentoxy group, n-hexoxy group, allyloxy group, and the like.

In the general formula (1), R+, Rz, R3, Rs, R
The alkylthio group represented by 6 and R9 is not particularly limited and any known alkylthio group can be used, but it generally has 1 to 1 carbon atoms.
Six straight-chain or branched saturated or unsaturated groups are preferred. Specific examples of the alkylthio group that are preferably used include methylthio group, ethylthio group, n-propylthio group, t-butylthio group, n-pentylthio group,
Examples include n-hexylthio group and allylthio group. Furthermore, in the general formula, the alkoxyalkyl group represented by R8, 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 alkoxyalkyl group include methoxymethyl group, methoxyethyl group, ethoxymethyl group, n-propoxymethyl group, t-butoxyethyl group, and allyloxyethyl group. Furthermore, in the general formula, the alkylthioalkyl groups represented by R+, Rz, and R3 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, butylthioethyl group, and allylthioethyl group.

Further, in the above general formula, the alkenyl groups represented by R5, R6 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 2 to 4. Specific examples of the alkenyl group include vinyl group, allyl group, 1so-propenyl group, 2-butenyl group, and 3-butenyl group. 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, but the number of carbon atoms is 2 to 4 as above.
It is preferable that the number of Specific examples of the alkynyl group include ethynyl group, 2-propynyl group, and the like.

In the above N-substituted-chloroacetanilide, 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 R1, R, and R7 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups. Even when used at a lower concentration than that, it not only has an excellent herbicidal effect that completely kills annual weeds such as field weeds and perennial weeds such as water cypress, but also
Since it is completely harmless to rice even when used at a high concentration of g/lOa, it is suitably used in the present invention. In particular, at least one of R1-R3 is a substituent other than a hydrogen atom, and this substituent is one CH bonded to the thiophene ring.
- is substituted at the ortho position, R4 is a hydrogen atom,
Furthermore, at least two of R6-R7 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. ,
It 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), we observed a characteristic absorption based on the CH bond (absorption) near 3150-2800 cm-', and a characteristic absorption based on the carbonyl bond of the amide group near 1680-1660 cm-'. I can do it.

(b) Measure the mass spectrum (MS) and calculate each peak observed (generally, the ion mass number m is expressed as the ion charge number e).
By calculating the composition formula corresponding to the value expressed by m/e divided by m/e, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule. In other words, the molecular weight of the compound subjected to the measurement can be determined because the intensity ratio is observed according to the isotope abundance ratio according to the number of halogen atoms in the measurement ← the sample subjected to the measurement. Furthermore, a characteristic strong peak shown in the general formula (1) and partially corresponding to R+ was observed, allowing the bonding mode of the molecule to be known.

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

(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 ppm, and this can be attributed to the methylene group (h) in the chloroacetyl group. A singlet corresponding to two protons was observed at 4.75 ppm, which is a methylene group (C)
It can be attributed to A quartet corresponding to two protons was observed at 6°67ppa+, and this can be attributed to protons (al, (bl) substituted on the thiophene ring. Three protons at 6.95 to 7.30 ppn+). A multiplet corresponding to is observed, and this can be attributed to the protons (el, (f), (a) substituted with the phenyl group.

Summarizing the 'H-NMR characteristics of the N-substituted-chloroacetanilide represented by the general formula (I) above, the methylene proton of the chloroacetyl group is usually 3.6 to 3.8
Appears as a singlet near ppm, and when R6 is a hydrogen atom, the methylene proton of the aminomethylene group is 4.7~
A single line near 5.0 ppm (however, a double line 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.
．． 7 ppm, the proton on the thiophene ring side is 5.8~
7.4ppa+, the protons on the benzene side are 6.0-7
．． It tends to show a characteristic peak at 7 ppm.

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

Further, N-substituted-chloroacetanilide includes R+, Rz, R3, R4, Rs, R& 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. 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 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 almost insoluble in water.

The method for producing the N-substituted-chloroacetanilide represented by the general formula (1) is not particularly limited. A typical manufacturing method is described below. General formula (where R, R, 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 represents a group, R, 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. ) and the general formula 〇 j! CH
By reacting with chloroacetyl halide represented by zCOX (wherein, X represents a halogen atom), the N-substituted-
Chloroacetanilide can be obtained.

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

In the reaction between the compound represented by the general formula (I[) and chloroacetyl halide, the molar ratio of the compound to be added may be appropriately determined as necessary, but it is usually the same mole or a slight excess of chloroacetyl halide. It is common to use moles.

Further, in the above reaction, hydrogen halide is produced as a by-product. Since this hydrogen halide reacts with the aniline derivative represented by the general formula (III) in the reaction system and causes a decrease in the yield of the product, a hydrogen halide scavenger is usually coexisted in the reaction system. The hydrogen halide scavenger, which is preferred, 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 monosodium 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. Nitriles; N,N-dialkylamides such as N,N-dimethylformamide and 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 (III) 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 0°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 desired product, ie, the N-substituted-chloroacetanilide represented by the general formula CI) from the reaction system, is not particularly limited and any known method can be employed. For example, the reaction solution is cooled or allowed to cool naturally to return to room temperature or near room temperature, the reaction solvent and the remaining hydrogen halide scavenger are distilled off, and the residue is extracted with benzene. In the above operation, the salt and high molecular weight compound produced from the by-produced hydrogen halide and the hydrogen halide scavenger are separated. The benzene layer is dried with a desiccant such as Glauber's salt or calcium chloride, and then benzene is distilled off and the residue is vacuum distilled to obtain the desired product. In addition to 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 (wherein R,, Rz and R3 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, alkylthioalkyl groups, and R4 represents a hydrogen atom or an alkyl group) shows,
X represents a halogen atom. ) and a substituted thiophene represented by the general formula R? (However, in the formula, R, , R, and R7 represent the same or different hydrogen atoms, halogen atoms, alkoxy groups, and alkylthio groups.) By reacting with chloroacetanilide represented by the general formula (1) )
-Substituted-chloroacetanilide can be obtained.

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

In addition, the conditions and isolation and purification method for carrying out this reaction are almost the same as those used in the reaction of the aniline derivative represented by the general formula (DI) and chloroacetyl halide as described above. Similar conditions can be adopted.

The N-substituted-chloroacetanilide represented by the above general formula (I) has a wide herbicidal spectrum against annual weeds such as field weeds, fireflies, and grasshoppers that occur in rice fields, as well as perennial weeds such as Omodaka. It is an excellent herbicide that can efficiently control paddy rice without causing chemical damage.

The other component of the herbicide composition of the present invention has the following general formula [■]
, Ra Rr + (However, in the formula, R8, R1, R1, R1, R1□ and RI
3 represents the same or different hydrogen atom, halogen atom, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, alkylsulfinyl group, alkoxycarbonyl group, carboxyl group, or a base thereof. ) is a diphenyl ether derivative represented by

In the above general formula (If), R11,R,,R,R1R
The alkyl group represented by I2 and R11 is not particularly limited in the number of carbon atoms, 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,
Examples include n-propyl group, iso-propyl group, n-butyl group, 1so-butyl group, 5ec-butyl group, t-butyl group, and the like.

In addition, in the general formula (n), Re, R9, R+ O%
Examples of the substituted alkyl groups represented by Rr + -, Rr z and RI3 include those in which one or more of the hydrogen atoms of the alkyl groups mentioned above are substituted with a substituent such as a halogen atom. The number of carbon atoms in the alkyl group is not particularly limited, and any alkyl group can be used. Among these, those having 1 to 4 carbon atoms are preferred. Preferred substituted alkyl groups in the present invention include fluoromethyl group, chloromethyl group, bromoethyl group, iodopropyl group, chlorobutyl group, difluoromethyl group, dichloroethyl group, dibromopropyl group, trifluoromethyl group, trichloro Examples include methyl group, tribromopropyl group, pentafluoroethyl group, and the like.

In addition, in the above general formula [■], R8, R1, RIG, R1
Examples of the halogen atom represented by 1% RI□ and R1 include fluorine, chlorine, bromine, and iodine atoms.

Furthermore, in the above general formula [■], R11, R1, R1
°, RI 1% The number of carbon atoms of the alkoxy group represented by RIt and RI3 is not particularly limited, but those having 1 to 4 carbon atoms are preferred from the viewpoint of easy availability of raw materials. Suitable alkoxy groups in the present invention include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, and t-butoxy groups.

In addition, in the general formula (n), R8, R9, RIG, R1
Examples of the substituted alkoxy group represented by 1% Lt and R13 include those in which one or more of the hydrogen atoms of the alkoxy group described above are substituted with a substituent such as an alkoxy group or an alkoxyalkoxy group. The number of carbon atoms in the alkoxy group or alkoxyalkoxy group as a substituent of the substituted alkoxy group is not particularly limited, and any group can be used. Among these, those having 1 to 8 carbon atoms are preferred. Preferred substituted alkoxy groups in the present invention include methoxy 1 methoxy group, ethoxymethoxy group, n-propoxymethoxy group, 1so
-butoxymethoxy group, methoxymethoxymethoxy group,
ethoxymethoxymethoxy group, ethoxyethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, is
Examples include o-propoxyethoxy group, t-butoxyethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group, ethoxyethoxyethoxy group, and the like.

Furthermore, in the general formula (n), R11, R9, RIG, R
Examples of the alkylsulfinyl group represented by RI□ and R13 include methylsulfinyl group, ethylsulfinyl i, n-propylsulfinyl group, iso-propylsulfinyl group, n-butylsulfinyl i, 1so
-butylsulfinyl group, t-butylsulfinyl group, etc.

Furthermore, R1, R,,R,. , RI2 and R
The alkoxycarbonyl group represented by 11 is not particularly limited in its carbon number, and any group can be used. Among these, those having 2 to 5 carbon atoms are preferred. Suitable alkoxycarbonyl groups in the present invention include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, 1so-propoxycarbonyl group, n
-butoxycarbonyl group, 1so-butoxycarbonyl group, 5eC-butoxycarbonyl group, t-butoxycarbonyl group, and the like.

In addition, in the general formula (n), RIl, R,, R10%
Examples of the metal forming the base of the carboxyl group represented by R11, R12, and R13 include alkali metals such as lithium, potassium, and sodium.

Among the diphenyl ether derivatives represented by the above general formula (n), R11, R9 and RIo are at the 2-position of the phenyl group,
It is a chlorine atom substituted at the 4th and 6th positions, and RIl and R
A compound/substance in which I2 is a hydrogen atom, R11 is a nitro group substituted at the 4° position of the other phenyl group, R6 is a hydrogen atom, and R7 and R1° are the 2nd and 4th positions of the phenyl group.
A compound in which R11 is a hydrogen atom, R, □ is a methoxy group substituted at the 3' position of the other phenyl group, and R13 is a nitro group substituted at the 4' position. and R3 is a hydrogen atom, R, and RIO
are chlorine atoms substituted at the 2- and 4-positions of the phenyl group, R11 is a hydrogen atom, and R1□ is a methoxycarbonyl group substituted at the 3'-position of the other phenyl group,
Compounds in which RI3 is a nitro group substituted at the 4' position are preferably used because they have little phytotoxicity (and high herbicidal activity).

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

The diphenyl ether derivative represented by the above general formula [■] exhibits a strong browning effect on annual broad-leaved weeds such as wild grasses and annual broad-leaved weeds such as Japanese azalea and Japanese azalea when germinated, but has no herbicidal effect on other perennial weeds such as A. It has the property of being small.

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 (r) and the diphenyl ether derivative represented by the general formula (If). It will be done.

However, the ratio of the diphenyl ether derivative to 1 part by weight of N-substituted chloroacetanilide is generally in the range of 0.01 to 50 parts by weight. More preferably, 1 to 2 parts of diphenyl ether derivative is added to 1 part by weight of N-substituted chloroacetanilide.
By setting the amount to 0 parts by weight, the herbicidal effect becomes even more excellent.

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

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

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

The herbicidal composition of the present invention may be sprayed as a raw material itself, or may be sprayed as a preparation prepared by mixing 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 in coarse powders, fine granules, granules, wettable powders, emulsions, flowable preparations, oil suspensions, etc.

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

Examples of solid carriers preferably used in the present invention are as follows. For example, clays represented by kaolinite group, montmorillonite group, attapulgite group, or gicrite; talc, mica, phyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium, lime, phosphorus. Inorganic substances such as ashstone, zeolite, silicic anhydride, and synthetic calcium silicate; Vegetable organic substances such as soybean flour, tobacco powder, walnut powder, 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 resins, ester gums, copal gums, and dammar gums; waxes such as cartebal 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, 0-chlorotoluene; ethers such as dioxane and tetrahydrofuran; acetone,
Ketones such as methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; Esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, n
-Alcohols such as hexanol, ethylene glycol and diethylene glycol; ether alcohols such as ethylene glycol phenyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Furthermore, in the preparation of the formulation in the present invention, conventionally known surfactants are used for the purposes of emulsification, dispersion, wetting, spreading, binding, disintegration control, active ingredient stabilization, flowability improvement, rust prevention, etc. It can be used without any restrictions. As surfactants, nonionic,
Although cationic, anionic and amphoteric ones are used, nonionic and/or anionic ones are usually preferred. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; those obtained by polymerizing and adding ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid; stearyl phosphate, dilauryl phosphate, mono- or dialkyl Polymerized addition of ethylene oxide to phosphoric acid; dodecylamine,
Products obtained by polymerizing and adding ethylene oxide to amines such as stearic acid amide; products obtained by polymerizing and adding ethylene oxide to higher fatty acid esters of polyhydric alcohols such as sorbitan; products obtained by polymerizing and adding ethylene oxide and propylene oxide; dioctyl succinate, etc. Examples include esters of polyhydric fatty acids and alcohols.

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. ;Arylsulfonates 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, 10 parts by weight of a diphenyl ether derivative and 1 part by weight of N-substituted chloroacetanilide are dissolved in an organic solvent, and a surfactant and a carrier are added to the solution and thoroughly mixed by pulverization. There is a method of obtaining a wettable powder by removing the organic solvent after that.

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

Furthermore, as a specific method for preparing granules, for example, 10 parts by weight of a diphenyl ether derivative, 1 part by weight of N-substituted chloroacetanilide, a surfactant and water are thoroughly kneaded, and then a carrier and a surfactant are mixed together. In addition, 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. That is, the herbicidal composition of the present invention exhibits excellent herbicidal effects against perennial weeds such as cyperus spp. be effective. Therefore, the herbicidal composition of the present invention
It has a broader herbicidal spectrum than that of its constituent components alone.

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

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

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

N-[2″-(5′-bromo)-chenylmethyl]-
2,6-dimethylaniline 1,81 g (6,14X
10-3 mole) was dissolved in 40mj2 of benzene and 0.81g of triethylamine (7,98X 10-"m
ole) and placed in ice water. Then 0.83 g of chloracetyl chloride (7,37xlO mol
The benzene solution (15 ml) of e) was slowly added. 3
After stirring for 1 hour, the mixture was heated at 50°C for 1 hour.

After cooling the reaction mixture to room temperature, 50 m of water 4.2N-
It was washed successively with 50 mf of hydrochloric acid and then with 50 ml of water, and the benzene layer was dried over anhydrous sodium sulfate. After that, it was purified by column chromatography and a yellow solid 1. t 3 g
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-'. Its elemental analysis value is C48,43
%, H4.05%, N3.99%, C+5H1
It was in good agreement with the calculated values for sNSOB, C1 (372,71): C 48.20%, H4, 32%, N 3.75%.

Also, when we measured the mass spectrum, m/e371
The molecular ion e corresponding to the molecular weight
■ Mbeek (M), m/e 336 to M-m/e
Each peak corresponding to 143 (100%) is shown.

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

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

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

In Table 1, the general formula (%) is represented by the general formula (CI). In addition, in the formulation examples and examples, N-substituted-chloroacetanilide is the compound number in the synthesis side [(1) to (66)]
The diphenyl ether derivative is represented by the following symbol ([
A] to (N).

The following is a combination example of Yokame 1 Compound (10 parts by weight of A3, 2 parts by weight of compound (1), surfactant Tsurupol 800A (trademark of Toho Chemical Industries)) 1.
A wettable powder was obtained by thoroughly pulverizing and mixing 5 parts by weight of surfactant detergent 60 (Lion Oil & Fat ■ Trademark) and 85 parts by weight of Zikrite.

Formulation example 2 10 parts by weight of compound (A), 5 parts by weight of compound (17),
15 parts by weight of the surfactant Tsurupol 5M100 (trademark of Toho Chemical Industries) and 70 parts by weight of xylene were thoroughly mixed to obtain an emulsion.

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

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

Example 1 A Wagnerbot with an area equivalent to 1/5000 are filled with water-mixed paddy soil, and seeds of broad-leaved weeds such as Japanese grasshopper, 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. embedded with tubers. Furthermore, three rice seedlings (cultivar name: Akinishiki) at the 2.5 leaf stage were planted at a depth of 2CII+. Thereafter, the rice was grown in a glass room at 20-25℃ under warm water conditions of about 3CI11, and 7 days after transplanting the rice (when the wildflowers were at about 0.8 leaf stage) and 14 days later (when the wildflowers were at about 2 leaf stage). A 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 Paddy rice chemical damage weed suppression rate (%) -2 normal 5:100 (complete withering) ±; slight damage 4 near 5-9
9 +: Minor damage 3: 50-74
廿: Nakayori 2: 25-49 1: 1-24 0: O (no effect observed at all)

[Brief explanation of drawings]

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

Claims (1)

[Claims] The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Represents an alkyl group or an alkylthioalkyl group, R_4 represents a hydrogen atom or an alkyl group, and R_5, R_6, and R_7 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio (indicates a group) and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_8, R_9, R_1_0, R_1_1
, R_1_2 and R_1_3 represent the same or different hydrogen atoms, halogen atoms, nitro groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, alkylsulfinyl groups, alkoxycarbonyl groups or carboxyl groups, or bases thereof. ) A herbicidal composition comprising a diphenyl ether derivative represented by the following as an active ingredient.