JPS61148103A - Herbicidal composition - Google Patents

Abstract

PURPOSE:A herbicidal composition, containing an N-substituted-chloroacetanilide and a fluorine-containing propionic acid derivative as active constituents, having a wide weeding spectrum, capable of exhibiting improved herbicidal activity, and highly safe for crops. CONSTITUTION:A herbicidal composition containing (A) a compound expressed by formula I (R1-R3 are H, halogen, alkyl, alkoxyl, alkylthio, etc.; R4 is H or alkyl; R5-R7 are H, halogen, alkyl, alkynyl, alkenyl, alkoxyl or alkylthio) and (B) a compound expressed by formula II [R8 and R9 are H or halogen; R10 is OR11, NR12R13, O<->N<+>R14R15R16R17 or O(M)n (R11-R17 are H or alkyl; M is alkali or alkaline earth metal; n is 1 when m is monovalent or 1/2 when M is bivalent)] in an amount of 0.01-50pts.wt., preferably 0.1-10pts.wt. based on one pts.wt. compound (A). The composition is capable of exhibiting improved herbicidal effect on perennial weeds, e.g. water nutgrass or arrowhead, on which the single compound has little effect.

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 fluorine-containing propionic acid derivative as active ingredients.

[Problems to be solved by the prior art and the invention: The following four properties 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 an excellent herbicide that satisfies the above-mentioned properties using the following general formula % (where R8 represents a halogen atom, an alkoxy group, an alkylthio group, an alkoxyalkyl group, or an alkylthioalkyl group, 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,
Rs, Rh and R7 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups. ) has already been proposed (Japanese Patent Application No. 58-111077 and others).

On the other hand, when the purpose is generally to kill weeds, 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 good and low-toxic herbicides are, if they are used in amounts far exceeding the appropriate amount required for the above-mentioned purposes, they tend to cause chemical damage to crops. 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 provided a herbicidal composition which has a wider herbicidal spectrum and is safer for crops in the use of N-substituted-chloroacetanilide represented by the above general formula as a herbicide. As I continued my research,
A herbicide composition containing a specific N-substituted chloroacetanilide and a specific fluorine-containing propionic acid derivative as active ingredients exhibits excellent herbicidal activity and is extremely safe for crops. I found out. 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), cocozcl (wherein Rr-, Rz and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups or alkylthioalkyl groups) , R4 represents a hydrogen atom or an alkyl group, and R2, R, and R1 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups.) N-substituted-chloroacetanilide represented by the following general formula [■] [However, in the formula, R1+ and R7 are the same or different hydrogen atoms or halogen atoms, and RIO is -OR+t.

N R+□R+ff, 0ONORIJRISRI6
RI7, or -〇(M)rl (However, R1, RI21
RI:II RI41RI9. RI6 and RI'7 are the same or different hydrogen atoms or alkyl groups, M is an alkali metal or alkaline earth metal, n is M is 1
When M is valent, it is 1, and when M is divalent, it is 1/2.

). ] A herbicidal composition characterized by containing a fluorine-containing propionic acid derivative represented by the following 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 I).

The following margins (However, in the formula, R+, Rz, and R3 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups, and R4 represents a hydrogen atom or an alkyl group. and Rs, Rh, and R1 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups.) N-substituted- represented by the above general formula (1) A small portion of chloroacetanilide, i.e. 2 of the thiophene ring
position and -CH- are bonded, R is a hydrogen atom or an alkyl group, RZ, R3 and R4 are hydrogen atoms,
Compounds in which R3 is an alkyl group, R6 is a hydrogen atom, an alkyl group, or an alkoxy group, and R1 is a hydrogen atom, an alkyl group, or a halogen atom are disclosed in U.S. Patent No. 39
No. 01917. However, most of the others are new compounds.

In the general formula (1), R1, RZ, R3, R5, R6
Specific examples of the halogen atom represented by R7 and R7 include chlorine, bromine, fluorine, and choraline atoms. Furthermore, in the general formula, RI, Rt, R:I, Ra, 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 preferably 1 to 6. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 1so-
Examples include propyl group, n-butyl group, 1so-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and the like. In the general formula (1), RI, Rz, R3, R1, R
The alkoxy group represented by 5 and R is not particularly limited, but a linear or branched saturated or unsaturated group having 1 to 6 carbon atoms is generally preferred. Specific examples of the alkoxy group that are generally preferably used include methoxy group, ethoxy group, n-propoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, allyloxy group, and the like.

In the general formula (1), RI, Rz, R3, Rs, R
The alkylthio group represented by 6 and R7 is not particularly limited and any known alkylthio group can be used, but 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 above general formula, the alkoxyalkyl group represented by R1, R2 and R:l is not particularly limited in the number of carbon atoms, but may be a linear or branched saturated or unsaturated group having 2 to 6 carbon atoms. Specific examples of suitable alkoxydialkyl groups include methoxymethyl group, methoxyethyl group, ethoxymethyl group, n-propoxymethyl group, t-butoxyethyl group, and allyloxyel group. Furthermore, in the general formula, the alkylthioalkyl groups represented by R+, Rz and R1 are not particularly limited in number of carbon atoms,
Straight chain or branched saturated or unsaturated groups having 2 to 6 carbon atoms are preferred, and specific examples of the alkylthioalkyl group include methylthiomethyl group, methylthioethyl group, ethylthiomethyl group, n -propylthiomethyl group, t-butylthioethyl group, allylthioethyl group, and the like.

Furthermore, in the general formula, Rs, Rh and R? The alkenyl group represented by is not particularly limited in the number of carbon atoms, regardless of whether it is linear or branched. 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 a vinyl group, an allyl group, a 1so-propenyl group, a 2-butenyl group, a 3-butenyl group, and the like. Furthermore, in the general formula, R5, R& and R? The alkynyl group represented by is 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, R9 is a halogen atom, an alkoxy group, an alkylthio group, an alkoxyalkyl group, or an alkylthioalkyl group,
R2 and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups,
R4 is a hydrogen atom or an alkyl group, and Rs, Rh, and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups. Even when used at a lower concentration, it not only has an excellent herbicidal effect that completely kills annual weeds such as field weeds and perennial weeds such as waterweed, but also has a
Since it is completely harmless to rice even when used at a high concentration of g/a, it is suitably used in the present invention. In particular, at least one of R and ~R3 is a substituent other than a hydrogen atom, and this substituent is one CH bonded to the thiophene ring.
- Substituted at the ortho position, R4 is a hydrogen atom,
Furthermore, at least two of R1-R1 are substituents other than hydrogen atoms, and these substituents are at the 2- and 6-positions of the phenyl group.
N-substituted chloroacetanilide substituted at this position is particularly preferably used because it has the above-mentioned properties.

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), it is possible to observe an absorption based on the CH bond near 3150-2800 am-' and a characteristic absorption based on the carbonyl bond of the amide group near 1680-1660 CI11-1. 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, when a sample subjected to measurement is expressed by the general formula (1), the molecular ion peak (hereinafter abbreviated as MO) generally has an intensity ratio according to the isotopic abundance ratio depending on the number of halogen atoms contained in the molecule. Because it is observed in
The molecular weight of the compound subjected to measurement can be determined.

Furthermore, for the N-substituted-chloroacetanilide represented by the general formula (1), peaks such as MG-Off, MO-COC)12(J and I) are observed, and the bonding mode of the molecule can be known.

(c) By measuring the lH-nuclear magnetic resonance spectrum ('H-NMR), it was determined that N
-You can know the bonding mode of hydrogen atoms present in -substituted-chloroacetanilide. 'H-NMR of N-Wta-chloroacetanilide represented by the above general formula (1)
(δ, ppm: based on tetramethylsilane, in deuterated chloroform solvent)
The 'H-NMR diagram of -dimethylanilide is shown in FIG. 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, and this can be attributed to the methylene group (h) in the chloroacetyl group. A singlet corresponding to 1 for 2 protons was observed at 4.75 ppm, and this can be attributed to the methylene group (c). A quartet corresponding to two protons was observed at 6.67 ppm, and this can be attributed to protons (a) and (b) substituted on the thiophene ring. A multiplet corresponding to three protons was observed at 6.95 to 7.30 ppm, and these are the protons (e), (f), (g) substituted with phenyl groups.
).

Summarizing the 'H-NMR characteristics of the N-substituted-chloroacetanilide represented by the above-mentioned general formula CI), the methylene proton of the chloroacetyl group is normally 3.6 to
When R4 is a hydrogen atom in the vicinity of 3.8 ppm, the methylene proton of the aminomethylene group is a singlet of 4.7~
5. Near Oppm (however, if there is an asymmetric substituent at position 2.6 on the aniline side, it may appear as a double line), and if R1 is an alkyl group, methine of the aminomethine group. Proton is 5.7-6.7
In ppn, the proton on the thiophene ring side is 5.8~'y,
4 ppm, and the protons on the Hensen side are 6.0 to 1. lp
It tends to show a characteristic peak at pm.

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

In addition, N-substituted-chloroacetanilide includes R+, Rz, 'R3, R-, Rs, R in the general formula (1).
Although its properties differ somewhat depending on the types of h and R1, it is generally a pale yellow or yellow viscous liquid or solid at room 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 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 (1) is not particularly limited. A typical manufacturing method is described below. General formula (1) (However, in the formula, R, , R, and R3 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, or alkylthioalkyl groups, and R4 is hydrogen represents an atom or an alkyl group, R5, R, and R7 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups,
An aniline derivative represented by ) representing an alkoxy group or an alkylthio group and a general formula C1cH2CO
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 (II[) as a raw material can be obtained by any method.

In the reaction between the compound represented by the general formula CI [I] 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 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 (I[) in the reaction system and causes a decrease in the yield of the product, a hydrogen halide scavenger is usually coexisted in the reaction system. It is preferable to let The hydrogen halide scavenger is not particularly limited, and any known one can be used. Examples of the scavenger preferably used for the -5 shell include trialkylamines such as trimethylamine, triethylamine, and tripropylamine, pyridine, sodium alcoholade, and sodium carbonate.

It is generally preferable to use an organic solvent in the reaction. Examples of those preferably used as the solvent 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. Examples include nitrile [; 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 target product, ie, the N-substituted-chloroacetanilide represented by the general formula (1), from the reaction system is not particularly limited, and any known method can be employed. For example, the reaction solution is cooled or allowed to cool naturally to return to room temperature or near room temperature, the reaction solvent and the remaining hydrogen halide scavenger are distilled off, and the residue is extracted with benzene. In the above operation, the salt and high molecular weight compound produced are separated from the by-produced hydrogen halide and the hydrogen halide scavenger. 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 (1), the following method is also preferably employed.

General formula (wherein R1, R2, and R1 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, alkoxyalkyl groups, and alkylthioalkyl groups, and R4 represents a hydrogen atom or an alkyl group. show,
X represents a halogen atom. ) and a substituted thiophene represented by the general formula (wherein Rs, R& and R1 are the same or different hydrogen atoms, halogen atoms, alkyl groups,
Indicates an alkenyl group, an alkynyl group, an alkoxy group, and an alkylthio group. ) The N-substituted-chloroacetanilide represented by the general formula (1) can also be obtained by reacting with the chloroacetanilide represented by the formula (1).

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

In addition, the initial conditions, conditions, and isolation and purification method used in carrying out the reaction are those used in the reaction of the aniline derivative represented by the general formula (I[[) with chloroacetyl halide, and the isolation and purification method. Almost the same conditions as in the purification method can be adopted.

The N-substituted chloroacetanilide represented by the above general formula (1) is an excellent weed killer with a wide spectrum of herbicidal properties against annual weeds such as field weeds, bulrushes, and grasshoppers that occur in rice fields, as well as perennial weeds such as Omodaka. It is a drug.

The other component of the herbicide composition of the present invention has the following general formula [■
[However, in the formula, Rs and R7 are the same or different hydrogen atoms or halogen atoms, and R6° is -ORr + .

N RIZR13,0” N' R14R+sR+hR
+q, or -〇('M8 (however, R11+ R1□,
R11R141R1'i+ Rlh and RI? are the same or different hydrogen atoms or alkyl groups, M is an alkali metal or alkaline earth metal, n is l when M is monovalent, and 1/2 when M is divalent. be. ). ] It is a fluorine-containing propionic acid derivative represented by the following.

In the above general formula (n), examples of the halogen atoms represented by R8 and R9 include fluorine, chlorine, bromine, and iodine atoms.

In addition, in the general formula (n), Ro, RIZ, RI3, RI
4. The alkyl group represented by RIS, Rlh and R17 is not particularly limited in terms of the number of carbon atoms, and any alkyl group can be used. However, from the viewpoint of easy availability of raw materials, those having 1 to 20 carbon atoms are preferable, but especially R11+
R1□ and R11 have 1 to 5 carbon atoms,
Also, R141R+sr Rlh and R1? Regarding the carbon number, those having 1 to 15 carbon atoms are suitable. 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, t-butyl group, n- Examples include octyl group, n-decyl group, n-dodecyl group, and the like.

In addition, in the above general formula (n), the alkali metal represented by M includes lithium, sodium, potassium, etc.
Examples of alkaline earth metals include calcium, magnesium, barium, and the like.

However, when M is an alkali metal, n is 1, and when M is an alkaline earth metal, n is 1/2.

Among the fluorine-containing propionic acid derivatives represented by the above general formula (II), compounds in which Rs is a fluorine atom and R1 is a hydrogen atom, in particular, Ro is a hydrogen atom or a methyl group,
A compound that is a lower alkyl group such as an ethyl group, R1,
and a compound in which RT3 are both hydrogen atoms, R14+
RIL+ R16 and F2+t are both hydrogen atoms, or R+4 and RIS are hydrogen atoms, and RIS
and R1? Compounds in which M is an alkyl group having 10 to 20 carbon atoms, and compounds in which M is an alkali metal such as sodium or potassium are preferably used.

Fluorine-containing propion fI represented by the above general formula [II]
! As the method for producing the derivative, any known production method may be employed without any restriction.

The fluorine-containing propionic acid derivative represented by the above general formula (II) exhibits strong herbicidal activity against grasses, but does not have selectivity for paddy rice, so if the application amount is increased, it will It has the disadvantage that it causes phytotoxic damage to paddy field weeds, and that sufficient herbicidal effects on paddy field weeds cannot be obtained if the application amount is reduced. However, the present inventors found that the general formula (II
Surprisingly, the fluorine-containing propionic acid derivative represented by the formula (1) has a function as a phytotoxicity reducing agent that increases the safety of the N-substituted chloroacetanilide represented by the general formula (1) to crops, At the same time, we newly discovered that it has the property of expanding its herbicidal spectrum.

The herbicidal composition of the present invention comprises N-substituted-chloroacetanilide represented by the general formula (1) and the general formula (II
) shows an excellent herbicidal effect in a wide range of usage ratios with the fluorine-containing propionic acid derivatives, and is highly safe for crops6. Generally, the amount of the fluorine-containing propionic acid derivative is in the range of 0.01 to 50 parts by weight per 1 part by weight of acetanilide. More preferably, N-substituted-
By adding 0.1 to 10 parts by weight of the fluorine-containing propionic acid derivative to 1 part by weight of chloroacetanilide, the herbicidal effect and safety for crops will be even better.

When the herbicide composition of the present invention is used against wildflowers and paddy rice that are sown at the same time in paddy soil, 0.1 per are
When treated at a concentration of 1.5 g, germination of wild grass is completely inhibited, but paddy rice is not affected at all even when treated with 200 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. However, in that case, the concentration of the fluorine-containing propionic acid derivative is 0.1 to 20 g per are, preferably 0.
．． Preferably, the amount of active ingredient is 5 to 10 g.

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 including paddy fields, fields of various grains, beans, cotton, vegetables, orchards, lawns, pastures, tea gardens, mulberry gardens, forests, non-agricultural lands, etc. It is.

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, 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,
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 alkyd 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. 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, 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 thereto. Examples include esters of polyhydric fatty acids such as dioctyl succinate and alcohols, which are obtained by polymerizing and adding ethylene oxide and propylene oxide; and dioctyl succinate. Suitable anionic surfactants include, for example:
Alkyl sulfate ester salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt; alkyl sulfonates such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulfonate; sodium isopropylnaphthalene sulfonate and sodium methylene bisnaphthalene sulfonate. , sodium ligninsulfonate, sodium dodecylbenzenesulfonate, and other sulfonic acid salts; and sodium tripolyphosphate and other phosphates.

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

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

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

The method for preparing the formulation in the present invention is not particularly limited, and conventionally known methods can be used.

For example, as a specific method for preparing a wettable powder, 5 parts by weight of a fluorine-containing propionic acid derivative and 1 part by weight of N-substituted chloroacetanilide may be dissolved in an organic solvent, and a surfactant and a carrier may be added to the solution. There is a method of obtaining a wettable powder by removing the organic solvent after grinding and mixing.

For example, as a specific method for preparing an emulsion, 1 part by weight of a fluorine-containing teropionic acid 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, as a specific method for preparing granules, for example, 1 part by weight of a fluorine-containing teropionic acid derivative, 1 part by weight of N-substituted chloroacetanilide, a surfactant, and water are thoroughly kneaded, and then a carrier and There is a method of obtaining granules by adding a surfactant, stirring well, extruding to a predetermined particle size, and drying.

〔effect〕

The herbicidal composition of the present invention described above exhibits a herbicidal effect that cannot be expected from the properties of each component alone. In other words, the herbicidal composition of the present invention can be used against perennial weeds such as staghorn cyperus and urticaria, for which neither the N-substituted chloroacetanilide nor the fluorine-containing propionic acid derivative can be expected to have much herbicidal effect when used alone. exhibits excellent herbicidal effects. In addition, fluorine-containing propionic acid derivatives act as phytotoxic agents for N-substituted chloroacetanilides, and as a result, they have a high degree of safety for crops, and are especially effective when applied to direct-seeded paddy rice cultivation. Demonstrate and do.

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-i! Synthesis of chloroacetanilide (synthesis example 1) N-(2'-(5'-bromo)-chenylmethyl)-2
,6-dimethylaniline 1.81g (6,14×10
1+*ole) in benzene 40n+4+ and triethylamine 0.81 g (7,98X 10-'m
ole) and placed in ice water. Next, 0.83 g of chloroacetyl chloride (7,37xlO-comol
A benzene solution (15 nL) of e) was gradually added. 3
After stirring for an hour, the mixture was heated at 50° C. for 1 hour. After cooling the reaction mixture to room temperature, 50 IIll of water, 50 Ill of 2N hydrochloric acid were added.
The benzene layer was washed successively with 0IIll, Vt and 501I11 of water, and the benzene layer was dried over 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 am-1. Its elemental analysis value is C4B, 4
3%, H4.05%, N3.99%, and Cl5H
It was in good agreement with the calculated values for C 48.20%, H 4, 32%, and N 3.75% for +5NSOBrC1 (372,71).

Also, when we measured the mass spectrum, m/e371
The molecular ion peak (MO) corresponding to the molecular weight, m/e
peak corresponding to MO-cl at 336, m/e 29
MO-COCHwCI for 3! The peak corresponding to m/e
Each peak corresponding to 143 (100%) is shown.

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

From the above results, it is clear that the isolated product is N-(2'-(5'-bromo)-chenylmethyl]-N-chloroaceto-2,6
-Simethylanilide (hereinafter abbreviated as compound (1))
It became clear that.

The yield was 49.5% (3
,04X 10-3 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 %formula% is the above general formula (1) R.

R.

S means.

Next, formulation examples and implementation of the herbicide composition of the present invention [(1)
~(66) ), and the fluorine-containing propionic acid derivatives are represented by the following symbols (A) to (L).

Formulation Example 1 Compound [A] 1 part by weight, Compound (1) 2 parts by weight, Surfactant Tsurupol 800A (Toho Chemical Industry ■ Trademark) 1.
A wettable powder was obtained by thoroughly pulverizing and mixing 5 parts by weight of the surfactant Detardient 60 (Lion Oil ■ Trademark) and 94 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 Compound [A12 parts by weight, Compound (39) 10 parts by weight,
4 parts by weight of dioctyl succinate, 4 parts by weight of sodium tripophosphate, 40 parts by weight of bentonite and 49 parts by weight of talc were mixed and pulverized, water was added and kneaded, then granulated and dried, and sized to 14 to 32 mesh. Granules were obtained.

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

Example 1 A Wagnerbot with an area equivalent to 1/5000 area was filled with water-mixed paddy soil, and seeds of broad-leaved weeds such as Japanese grasshopper, Japanese cypress, bulrush and other broad-leaved weeds were sown on the surface layer of the soil. embedded with tubers. Furthermore, 3 rice seedlings (cultivar name: Akinishiki) at the 2.5 leaf stage were planted at a depth of 'lam'. Thereafter, the rice was submerged to a depth of about 3 cm and grown in a glass room at 20 to 25°C, and 7 days after transplanting (w1 when the wildflowers were at about 0.8 leaf stage) and 14 days later (when the wild plants were at about 2 leaf stage). season)
Next, 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: Weed suppression rate (%) 5:100 (complete death) 4nia 5-99 3:50-74 2:25-49 1:1-24 0:0 (no effect observed) No chemical damage to paddy rice was observed at all.

Example 2 A Wagner bot equivalent to 1/5000 are was filled with watered and kneaded paddy soil, and wild grass was sown on the surface layer of the soil.
Furthermore, after sowing 100 rice seeds (cultivar name: calrose), they were grown in a glass room at 20 to 25°C under warm water conditions of approximately 3 cm, and 7 days after rice sowing (when the wildflowers were at the approximately 0.8 leaf stage). Next, 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 21 days after treatment with chemicals, the herbicidal effect of the grasshopper and the chemical damage caused to paddy rice were investigated. The results are shown in Table 3.

Weed suppression rate (%) of wild grass weeding effect 5:100 (Complete death) 4nia 5-99 3:50-74 2:25-49 1:1-24 0:0 (No effect observed at all) Also regarding paddy rice phytotoxicity The ratio of normally grown rice among 100 rice grains to the untreated plot was calculated and expressed on a 5-level scale from - to 10++.

Paddy rice chemical damage (%) 1: Normal (0) ±: Slight harm (1 to 10) +: Minor harm (11-29) ++: Medium harm (30-69) +++: Great harm (70-100) Margin below Table 3

[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 The N-substituted-chloroacetanilide represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R_8 and R_9 are the same or different hydrogen atoms or halogen atoms, and R_1_0 -OR_1_
1, -NR_1_2R_1_3, -O^■N^■R_1
_4R_1_5R_1_6R_1_7, or -O(M)
_n (However, R_1_1, R_1_2, R_1_3, R
_1_4, R_1_5, R_1_6 and R_1_7 are the same or different hydrogen atoms or alkyl groups, M is an alkali metal or alkaline earth metal, n is 1 when M is monovalent, and when M is divalent When , it is 1/2. )
It is. ] A herbicidal composition comprising a fluorine-containing propionic acid derivative represented by the following as an active ingredient.