JPH0615445B2 - Herbicide composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a herbicidal composition comprising an N-substituted-haloacetamide and a triazine derivative as active ingredients.

[Problems to be Solved by Prior Art and Invention]

There are the following four items as the properties essentially required for the herbicide. That is, one is safe for the crop, the other is
Firstly, it has a broad herbicidal spectrum required to completely kill many kinds of weeds growing in the crop growing area, and thirdly, the herbicide has long-term efficacy.
For one thing, it has a more effective herbicidal effect when applied in a small amount.

Conventionally, many compounds have been synthesized as chloroacetamide compounds, and some of them have been known to be useful as herbicides. For example, Japanese Patent Laid-Open No. 58-947 discloses a general formula (However, R ₅ is a hydrogen atom or an alkyl group, R ₆ is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyalkyl group, or a benzyl group, and R ₇ is a hydrogen atom, an alkyl group, or an alkenyl. A group, an alkoxy group, an alkoxyl group, or the like, X ₁ ,
X ₂ and X ₃ are independently of each other a hydrogen, fluorine, chlorine or bromine atom or a linear or branched alkyl group having 1 to 4 carbon atoms. ), N- (1-alkenyl) -cloacetanilide is described as being useful as a herbicide,
Regarding the compound in which R ₅ is an aryl group such as a phenyl group, no reported examples are found due to the difficulty of the production method.

[Means for solving problems]

The present inventors have been conducting synthetic research for a wide variety of compounds having excellent physiological activity for many years. In recent years, when we focused our attention on specific compounds having an enamine structure, especially haloacetylated vinylamine compounds, and conducted intensive research into their synthesis and physiological activity, we found that specific novel haloacetamide compounds produced various weeds in paddy fields and upland fields. On the other hand, they have found that they are extremely useful compounds that have excellent activity even at low concentrations and have no phytotoxicity to crops and toxicity to humans and livestock.

Then, as a result of repeated studies to further improve the herbicidal activity of the haloacetamide compound, a composition in which such a specific haloacetamide compound and a specific triazine derivative were combined was extremely unexpected from the individual properties. It has been found that the herbicidal activity is exerted, the herbicidal effect is high at a lower dose, and the herbicidal spectrum is wide, and the present invention is proposed.

The present invention has the following general formula [I] (However, X is a hydrogen atom, a halogen atom, an alkyl group,
An alkoxy group or a phenoxy group, R ¹ and R
² represents the same or different hydrogen atom or an alkyl group, and R ³ represents an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, or a phenyl group (in this case, an alkyl group, an alkenyl group, an alkoxy group and a halogen). An optionally substituted substituent selected from the group A), Y represents a chlorine atom or a bromine atom) and an N-substituted-haloacetamide compound represented by the following general formula (However, Z represents a chlorine atom or an alkylthio group.
In addition, R ⁴ and R ⁵ are the same or different alkyl groups and may have a cyano group as a substituent) and a triazine derivative represented by the formula (3) as an active ingredient. Is.

One component of the herbicidal composition of the present invention is N-substituted-haloacetamide represented by the following general formula [I].

(However, X is a hydrogen atom, a halogen atom, an alkyl group,
An alkoxy group or a phenoxy group, R ¹ and R
² represents the same or different hydrogen atom or an alkyl group, and R ³ represents an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, or a phenyl group (in this case, an alkyl group, an alkenyl group, an alkoxy group and a halogen). Y may be a chlorine atom or a bromine atom. ) The N-substituted-haloacetamide represented by the above general formula is a novel compound which was first synthesized by the present inventors and whose herbicidal activity was confirmed.

In the general formula [I], specific examples of the halogen atom represented by X include chlorine atom, bromine atom, fluorine atom and iodine atom. The alkyl group represented by X may be linear or branched, and the number of carbon atoms is not particularly limited, but the number of carbon atoms is preferably 1 to 6 from the viewpoint of easy availability of raw materials. Is. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. Further, the alkoxy group represented by X is not particularly limited, but in general, a linear or branched alkoxy group having 1 to 6 carbon atoms is suitable. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group and t-butoxy group.

The alkyl group represented by R ¹ and R ² in the general formula is not particularly limited, but preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group and an ethyl group.

As the alkyl group represented by R ³ in the above general formula, the alkyl groups exemplified for X are used without particular limitation. The alkenyl group represented by R ³ is not particularly limited, but preferably has 2 to 6 carbon atoms. Specific examples of the alkenyl group include a propenyl group, a butenyl group,
Examples thereof include alkenyl groups having positional isomers such as a pentenyl group. The alkoxyalkyl group represented by R ³ is not particularly limited, but preferably has 2 to 8 carbon atoms. Specific examples of the alkoxyalkyl group include methoxymethyl group, methoxyethyl group, dimethoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, Examples thereof include a propoxymethyl group, a propoxyethyl group, a propoxypropyl group, a butoxymethyl group, a butoxyethyl group and a pentoxyethyl group. The alkenyloxyalkyl group represented by R ³ is not particularly limited, but has 4 carbon atoms.
It is preferable that it is ~ 8. Specific examples of the alkenyloxy group include an alkenyloxy group having a positional isomer such as a propenyloxymethyl group, a butenyloxymethyl group, a pentenyloxymethyl group, a propenyloxyethyl group and a propenyloxypropyl group. Further, as the substituent of the phenyl group represented by R ³ ,
An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom and an alkenyl group are preferable. Specific examples of the substituted phenyl group include methylphenyl group, ethylphenyl group, propyl (methyl) phenyl group, dimethylphenyl group, diethylphenyl group, methyl (ethyl) phenyl group, chlorophenyl group, dichlorophenyl group, chloro (methyl) phenyl. Group, methoxyphenyl group, methyl (methoxy) phenyl group, ethyl (ethoxy) phenyl group, allylphenyl group, allyl (methyl)
Examples thereof include a substituted phenyl group having a positional isomer such as a phenyl group. For example, regioisomers of methylphenyl group include o-methylphenyl group, m-methylphenyl group,
And p-methylphenyl group, and examples of the dimethylphenyl group include 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, and 2,6-dimethylphenyl group.

The structure of the compound represented by the above general formula [I] of the present invention is
It can be confirmed by the following means.

(B) By measuring the infrared absorption spectrum (ir),
Absorption based on CH bond near 200-2800 cm ^-1 , 1680-1650c
Strong absorption due to the amide carbonyl group can be observed near m ^-1 .

(B) Mass spectrum (ms) was measured and each peak observed
(Generally, m that is obtained by dividing ion molecular weight m by ion charge number e
/ E for the mass number)
And the molecular weight of the compound used for measurement and the molecule.
You can know the bonding state of each atomic group inside. You
That is, the sample used for the measurementIn general, the molecular ion peak (hereinafter M When
Abbreviated) is the number of halogen atoms contained in the molecule
Depending on the intensity ratio according to the isotope abundance ratio,
The molecular weight of the compound used for the measurement can be determined.
Further, the compound of the present invention represented by the above general formula
Is M -Y, M −COCH₂Characteristic peak corresponding to Y
Is observed, and the binding mode of the molecule can be known.

By measuring the (c) ¹ H- nuclear magnetic resonance spectra ^{(1 H-nmr),} it is possible to know the binding mode of the hydrogen atoms present in the compounds of the present invention represented by the general formula.
¹ H-nmr (δ, p of the compound represented by the above general formula [I]
pm: Tetramethylsilane standard, in heavy chloroform solvent)
As a typical example of N- [1- (phenyl) ethenyl]-
The results of ¹ H-nmr analysis of N-chloroaceto-2 ', 6'-dimethylanilide are as follows.

That is, a singlet with 6 protons based on the methyl group (d) at 2.30 ppm, a singlet with 2 protons based on the chloroacetyl group (c) at 3.75 ppm, and an ethenyl group at 4.41 ppm and 4.97 ppm.
Two singlets corresponding to one proton based on (a) and (b), and multiple lines corresponding to eight protons based on a benzene ring were observed at 7.10 ppm to 7.60 ppm.

(D) Oxygen is obtained by obtaining each weight% of carbon, hydrogen, nitrogen, and halogen (or sulfur when sulfur is included) by elemental analysis, and further subtracting the total weight% of each recognized element from 100. You can calculate the weight% of
Therefore, the composition formula of the compound can be determined.

The haloacetamide compound of the present invention has a slightly different property depending on the types of X, R ¹ , R ² and R ³ , Y in the above general formula, and the degree of purification, but it is generally colorless to blackish at room temperature and normal pressure. It is a viscous liquid or solid. Specifically, it will be shown in Examples described later. The compound of the present invention is soluble in general organic solvents such as benzene, ether, alcohol, chloroform, acetonitrile, dimethylformamide and dimethylsulfoxide, but it is sparingly soluble in water.

The method for producing the compound represented by the above general formula [I] of the present invention is not particularly limited. A typical manufacturing method is described below.

(However, X is a hydrogen atom, a halogen atom, an alkyl group,
An alkoxy group or a phenoxy group, R ¹ and R ² represent the same or different hydrogen atom or an alkyl group, and R ³ represents an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, a substituted or unsubstituted phenyl Indicates a group. ) And a general formula YCH ₂ COZ (where Y is a chlorine atom or a bromine atom, Z is a chlorine atom, a bromine atom, Indicates. By reacting with a haloacetyl compound represented by the formula (1), the compound represented by the above general formula [I] can be obtained.

The Schiff base compound represented by the general formula [II], which is a raw material for the method, may be obtained by any method. Generally, it is obtained by dehydration condensation of a corresponding carbonyl compound and an amine compound as represented by the following formula.

In the reaction of the Schiff base compound represented by the general formula (II) and the haloacetyl compound, the charged molar ratio of both compounds may be appropriately determined as necessary, but usually equimolar amount or a slight excess of haloacetyl compound is used. Is common.

Since acidic products such as hydrogen halide are by-produced in the reaction, it is preferable to use an acidic component scavenger in the normal reaction. The type of the scavenger may be selected as appropriate according to the reaction conditions (solvent, temperature, etc.), and examples of the scavenger generally used include triethylamine, pyridine, sodium carbonate and the like.

In the reaction of the present invention, it is generally preferable to coexist with an organic solvent. Examples of those preferably used are benzene, toluene, xylene, hexane, petroleum ether, chloroform, methylene chloride, ethyl ether, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, acetonitrile, N, N-dimethylformamide, hexamethylphosphonate. Lamide, dimethyl sulfoxide and the like can be mentioned.

In particular, when using a polar solvent having a basicity such as N, N-dimethylformamide, N, N-dimethylacetamide, and hexamethylphosphoramide as a solvent for the reaction,
Without coexistence of a scavenger for hydrogen halide produced as a byproduct,
In many cases, the reaction proceeds easily and the desired haloacetamide compound can be obtained in a high yield, which is extremely preferable.

The order of adding the raw materials in the reaction is not particularly limited, but generally, the Schiff base compound represented by the general formula (II) is dissolved in a solvent, and the haloacetyl compound may be added with stirring.

The reaction temperature in the above reaction can be selected from a wide range, and is generally -20 ° C to 150 ° C, preferably -10 ° C to 12 ° C.
You can select it in the range of 0 ° C. The reaction time varies depending on the raw materials and the reaction temperature, but it is usually 5 minutes to 10 days, preferably 1 hour to 50 hours. Further, it is preferable to carry out stirring during the reaction.

The method for isolating and purifying the desired product, that is, the compound represented by the general formula [I] from the reaction system is not particularly limited, and a known method can be employed. For example, after the reaction, the reaction solvent and the hydrogen halide scavenger are distilled off, water is added, and the residue is extracted with benzene, ether, chloroform and the like. Further, the organic layer is dried with a desiccant such as sodium sulfate or calcium chloride, the solvent 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 be purified by chromatography, recrystallization and the like.

Furthermore, when the reaction is carried out using an amide-based polar solvent such as N, N-dimethylformamide as a reaction solvent, a hydrogen halide scavenger is often unnecessary, and a low-boiling substance is distilled off after the reaction is completed. Then, the desired product can be obtained by simply performing vacuum distillation. After the reaction is completed, water is added to the reaction solution, which is then extracted with benzene, ether, chloroform and the like, the organic layer is dried with a drying agent such as sodium sulfate, the solvent is distilled off, and the residue is vacuum distilled, The target product can also be obtained by purification by chromatography or recrystallization.

The compound represented by the above general formula [I] of the present invention exhibits remarkably excellent effects as a herbicide. For example, it exhibits an excellent herbicidal effect on soil treatment before and after germination of grass weeds, broad-leaved weeds, and perennial weeds. In particular, it shows a remarkable herbicidal effect on grass weeds, for example, it shows excellent herbicidal effects not only on its germination but also on plants grown at the 1.5-leaf stage not only to the severely damaging weeds.

Also, when used as a field herbicide, it exerts a selective herbicidal effect, so it should be applied to wheat, barley, corn, upland rice and other grass crops without damage, as well as broad-leaved crops such as soybeans, cotton and beets. You can Furthermore, it can be used as a herbicide for lawns as well as for paddy fields and uplands.

The other component of the herbicidal composition of the present invention is represented by the following general formula [II
I] (However, Z represents a chlorine atom or an alkylthio group.
R ⁴ and R ⁵ are the same or different alkyl groups and may have a cyano group as a substituent).

In the above general formula [III], the alkylthio group represented by Z is not particularly limited, but in general, a linear or branched alkylthio group having 1 to 6 carbon atoms is suitable. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group and an isopropyl group. Further, the unsubstituted alkyl group represented by R ⁴ and R ⁵ in the above general formula is not particularly limited, but in general, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group,
Examples thereof include an isopentyl group and a 1,2-dimethylpropyl group. The substituted alkyl group represented by R ⁴ and R ⁵ includes a methoxyethyl group, an ethoxyethyl group, a cyanoethyl group, a methylthioethyl group, a cyanopropyl group,
Examples thereof include a cyanobutyl group.

In the above general formula [III], Z is a methylthio group,
Those in which R ⁴ is an ethyl group and R ⁵ is an ethyl group or a 1,2-dimethylpropyl group are particularly suitable as a herbicide for paddy fields. In addition, Z is a methylthio group, R ⁴ is an ethyl group and R ⁵ is a t-butyl group, or R ⁴ and R ⁵ are both isopropyl groups; Z is a chlorine atom and R ⁴ is Those having an ethyl group and R ⁵ being an ethyl group, an isopropyl group, or a 1-cyanoisopropyl group are particularly suitable as a herbicide for upland fields.

The triazine derivative represented by the general formula [III] is a wide variety of broad-leaved weeds, for example, azalea, yellow cypress, eel,
It is known as an effective herbicide against ragweed, chickweed, barnyard grass, velvetleaf and the like. However, it has the property of having a small herbicidal effect on grass weeds and perennial weeds.

As a method for producing the triazine derivative represented by the general formula [III], a known production method can be adopted without any limitation.

The herbicidal composition of the present invention comprises the N-substituted-haloacetamide represented by the general formula [I] and the general formula [III]
And a triazine derivative represented by That is, the herbicidal composition of the present invention has a synergistic effect brought about by mixing the N-substituted-haloacetamide represented by the general formula [I] with the triazine derivative represented by the general formula [III]. As compared with the case of using the above composition alone, it shows the same or higher effect with a smaller application amount, and therefore it is an excellent herbicide from the viewpoint of preventing environmental pollution, which is becoming a problem in recent years. Moreover, it shows an extremely broad weed-killing spectrum against various kinds of weeds growing in fields, paddy fields, lawns, etc., and can kill or suppress these weeds for a long period of time.

An excellent herbicidal effect can be obtained in a wide range of use ratio of the N-substituted-haloacetamide represented by the general formula [I] and the triazine derivative represented by the general formula [III].
Among them, the usage ratio of both is 0.01 to 5 for the triazine derivative with respect to 1 part by weight of the N-substituted-haloacetamide.
It is generally in the range of 0 parts by weight. More preferably, the herbicidal effect is further improved by using 0.1 to 20 parts by weight of the triazine derivative with respect to 1 part by weight of N-substituted-haloacetamide.

When the herbicide composition of the present invention is used for Novier sown in paddy soil, treatment with a concentration of 0.2 g per areth completely inhibits germination of Novier, but 10
There is no effect even when treated with 0 g. Therefore, it is generally 0.15 to 200g, preferably 0.5 to 50g per are.
It can be used as an active ingredient in paddy fields.

When the herbicide composition of the present invention is used as a herbicide for field crops, it has an effect even before and after germination of weeds, and a high effect is obtained in soil treatment and foliage treatment,
Widely useful in fields such as various cereals, legumes, cotton, and vegetables. Even when the herbicidal composition of the present invention is used as a field-acting herbicide, germination is completely suppressed by treating, for example, Nobie or Mekishiba at a concentration of 0.5 g per are. Therefore, it is generally 0.2g-500 per are.
g, preferably 1 g to 200 g, may be used in the field as an active ingredient amount.

Furthermore, since the herbicidal composition of the present invention has a high degree of safety against lawns, and the efficacy is connected, the herbicidal composition is currently applied to very large area lawns such as golf courses 3 to 4 times. Compared with the above herbicide application method, it is desirable in terms of labor and economy, and its usefulness as a lawn herbicide is extremely large.

The herbicide composition of the present invention may be sprayed on the drug substance itself, or may be sprayed as a preparation prepared by mixing it with a carrier and, if necessary, other auxiliary agents. The formulation form is not particularly limited, and conventionally known formulation forms are used. For example, powder,
It can be prepared and used as a coarse powder, fine granule, granule, wettable powder, emulsion, flowable preparation, oil suspension and the like.

When preparing the herbicidal composition of the present invention into a preparation, a suitable solid carrier to be used may be any conventionally known solid carrier without any limitation. Examples of the solid carrier preferably used in the present invention are as follows. For example, clays typified by kaolinite group, montmorillonite group, attapulgite group or sieglite; talc, mica, pyrophyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth magnesium, lime, phosphorus lime, Inorganic substances such as zeolite, silicic anhydride, and synthetic calcium silicate; soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose, and other plant organic substances; coumarone resin, petroleum resin, alkyd resin, poly Examples thereof include synthetic or natural polymer compounds such as vinyl chloride, polyalkylene glycols, ketone resins, ester gums, copal gums, dammal gums; waxes such as carnauba wax and beeswax; and urea.

As the liquid carrier used in the present invention, any conventionally known liquid carrier can be used without any limitation. Examples of liquid carriers that are preferably used in the present invention are as follows. Paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene; carbon tetrachloride, chloroform, trichloroethylene, monochlorobenzene, Chlorine hydrocarbons such as o-chlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, Esters such as dibutyl maleate and diethyl succinate; alcohols such as methanol, n-hexanol, ethylene glycol and diethylene glycol; Chi glycol phenyl ether, diethylene glycol ethyl ether, ether alcohols such as diethylene glycol butyl ether; dimethylformamide, polar solvents or water such as dimethyl sulfoxide.

Further, in the preparation of the preparation of the present invention, a conventionally known surfactant for the purpose of emulsification, dispersion, wetting, mineralization, binding, adjustment of disintegration, stabilization of active ingredient, improvement of fluidity, rust prevention, etc. It can be used without any restrictions. As a surfactant, nonionic,
Cationic, anionic and zwitterionic ones are used, but usually nonionic and / or anionic ones are preferably used. Suitable nonionic surfactants are, for example, those obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; those obtained by polymerizing addition of ethylene oxide to aalkylphenols such as isooctylphenol and nonylphenol. Polymerized ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Polymerized ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid Polymerized addition: Styaryl phosphoric acid, dilauryl phosphoric acid also mono- or dialkyl phosphoric acid polymerized with ethylene oxide: Polymerized addition of ethylene oxide to amines such as silamine and stearic acid amide; Polymeric addition of higher fatty acid esters of polyhydric alcohols such as sorbitan and ethylene oxide thereto; Polymerized addition of ethylene oxide and propylene oxide; Dioctyl succinate Examples thereof include esters of polyvalent fatty acids such as nates with alcohols. Suitable anionic surfactants include, for example, sodium laurate, alkyl sulfate salts such as oleyl alcohol sulfate amine salt; alkyl sulfonate salts such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexenesulfonate. ;
Examples thereof include aryl sulfonates such as sodium isopropylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate; and phosphates such as sodium tripolyphosphate.

Further, in the preparation of the present invention, conventionally known auxiliary agents can be used without any limitation. The auxiliary agent is used for various purposes, and is also used for the purpose of enhancing the herbicidal effect by improving properties such as disintegration property of the granule. Examples of the auxiliary agent preferably used in the present invention are as follows. Casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose,
Examples thereof include polymer compounds such as methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol and the like.

The above carriers, surfactants and auxiliaries are the dosage forms of the formulation,
Depending on the application and the like, they may be used alone or in combination depending on the purpose.

The preparation method of the preparation in the present invention is not particularly limited, and a conventionally known method is used. For example, as one specific method for preparing a wettable powder, a triazine derivative 10
There is a method of obtaining a wettable powder by dissolving 1 part by weight and 5 parts by weight of N-substituted-haloacetamide in an organic solvent, adding a surfactant and a carrier to the solution and thoroughly pulverizing and mixing, and then removing the organic solvent.

Further, for example, as one specific method for preparing an emulsion, 10 parts by weight of a triazine derivative, 5 parts by weight of N-substituted-haloacetamide and 15 parts by weight of a surfactant are well mixed with a petroleum solvent such as xylene to obtain an emulsion. There is a way.

Furthermore, for example, as one specific method for preparing granules, 10 parts by weight of a triazine derivative, 5 parts by weight of N-substituted-haloacetamide, a surfactant and water are well kneaded, and then a carrier and a surfactant are added. In addition, after stirring well,
There is a method of obtaining granules by extruding to a predetermined particle size and drying.

[Effect]

The above-described herbicidal composition of the present invention exhibits a herbicidal effect that cannot be predicted from the properties of the individual components. That is, both the N-substituted-haloacetamide and the triazine derivative exert synergistically superior herbicidal effects as compared with the case where they are used alone. For example, for the perennial weeds of paddy fields, such as Pleurotus cornucopia and Urikawa, the herbicide of the present invention exerts a far superior herbicidal effect than the case where each of them is used alone. Further, when the herbicide of the present invention is used as a field-acting herbicide or a lawn herbicide, a far wider herbicidal spectrum is exhibited for a long period of time than when each is used alone. Furthermore, it has a greater herbicidal effect at the same level as the application rate of each component alone. Moreover, it is safe for crops.

Therefore, the herbicidal composition of the present invention sufficiently satisfies the properties required for a herbicide, and its utility is extremely large.

〔Example〕

Hereinafter, the herbicidal composition of the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

Example 1 4.57 g (0.020 mol) of N- (1-methylbenzylidene) -2 ', 6'-dimethylaniline was dissolved in 25 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF) and stirred at room temperature. Meanwhile, 2.48 g of chloroacetyl chloride (0.02
2 mol) of DMF in 5 ml was slowly added. After stirring at room temperature for a while, it was heated at 60 ° for 2 hours. After cooling the reaction solution to room temperature, it was washed twice with 100 ml of water,
The organic layer was extracted with 100 ml of sodium. The ether layer was dried over sodium sulfate, the ether was distilled off, and the obtained solid was recrystallized from a benzene / hexane mixed solvent to obtain 4.34 g of colorless crystals having a melting point of 91 to 92 ° C.

When the infrared absorption spectrum of the compound was measured, it was 3100.
～2800Cm ^-1 to based on C-H bond absorption, strong absorption based on the carbonyl bond of the amido group in 1680 cm ^-1, the 1615 cm ^-1 It showed a weak absorption based on.

Moreover, when the mass spectrum was measured, it was found to be m / e 299.
Child ion peak (M ), M to m / e 264 -Cl
Corresponding peak, M at m / e 222 −COCH₂Pi corresponding to Cl
, Etc.¹ H-nuclear magnetic resonance spectrum (δ; ppm: tetramethyl
Silane (TMS) standard, deuterated chloroform solvent)
It was The analysis results are as follows.

The elemental analysis values are C72.08%, H5.98%, N4.80%,
And the calculated value for the composition formula C ₁₈ H ₁₈ NClO ₂ (299.80) C 72.
It was in good agreement with 11%, H6.05% and N4.67%.

From the above results, it became clear that the isolated product was N- [1-phenyl) ethenyl] -N-chloroaceto-2 ', 6'-dimethylanilide. The yield was 71%. The compound No. of the compound is 1.

Example 2 N-[(1-phenyl-2,2-dimethyl) ethylidene]
2.06 g of −2′-methoxyethylamine was dissolved in 20 ml of DMF, and chloroacetyl chloride was added while stirring at room temperature.
1.52 g was added slowly. The reaction solution was heated at 60 ° C. for 2 hours and then cooled to room temperature, washed with water and an aqueous sodium carbonate solution, and the organic layer was extracted with ether. The ether layer was dried over sodium sulfate, and the viscous liquid obtained by distilling off the ether was purified by column chromatography (silica gel) to give a pale yellow viscous liquid 1.90.
g was obtained.

When the infrared absorption spectrum of the compound was measured, it was 3100.
～2800Cm ^-1 to based on C-H bond absorption of amide 1670 cm ^-1 Strong absorption based on 1600 cm ^-1 Absorption based on

Moreover, when the mass spectrum was measured, it was found to be m / e 281.
Child ion peak (M ), M to m / e 266 -CH₃Corresponding to
Peak, m at m / e 246 Peak corresponding to -Cl
Etc.¹ H-nuclear magnetic resonance spectrum (δ; ppm: tetmethyl
The run standard, deuterated chloroform solvent) was measured. That analysis
The results were as follows.

The elemental analysis values are C63.83%, H7.21%, N5.12%, and the calculated value C6 for the composition formula C ₁₅ H ₂₀ NClO (281.78).
It was in good agreement with 3.94%, H7.15%, N4.97%.

From the above results, the isolated product is N- [1-phenyl-2,
2- (Dimethyl) ethenyl] -N-chloroaceto-2 '
-Methoxyethylamide was found.
The yield was 67%. The compound No. of the compound is 2.

Example 3 N- [1- (p-phenoxyphenyl) -2-methylpropylidene] -2'-methoxyethylamine 2.18 g (0.
(0073 mol) was dissolved in 20 ml of DMF, and a solution of 1.03 g of chloroacetyl chloride in 5 ml of DMF was gradually added while stirring at room temperature. After stirring at room temperature for a while, the mixture was heated and stirred in an oil bath (50 ° C.) for 2 hours. The reaction solution was cooled to room temperature, washed twice with 100 ml of water, and the organic layer was extracted with 100 ml of ether. The ether layer was dried over sodium sulfate, and the viscous liquid obtained by removing the ether was purified by column chromatography (silica gel) to obtain 1.86 g of a colorless viscous liquid.

When the infrared absorption spectrum of the compound was measured, it was 3100.
～2800Cm ^-1 to based on C-H bond absorption of amide 1670 cm ^-1 It showed strong absorption due to binding.

Also, when the mass spectrum was measured, it was found to be m / e 373.
Molecular ion peak (M ), M to m / e 358 -CH₃Against
Corresponding peak, m at m / e 358 -Pie corresponding to Cl
Ku, to m / e 223The peaks corresponding to are shown.¹ H-nuclear magnetic resonance spectrum (δ; ppm: tetramethyl
The silane standard, deuterated chloroform solvent) was measured. The solution
The analysis results were as follows.

Its elemental analysis values are C67.41%, H6.45%, N3.71%, and the calculated value C67.24 for the composition formula C ₂₁ H ₂₄ NClO ₃ (373.87).
It was in good agreement with 46%, H6.47%, and N3.75%.

From the above results, it became clear that the isolated product was N- [1-p-phenoxyphenyl) -2,2- (dimethyl) ethenyl] -N-chloroaceto-2'-methoxyethylamide. The yield was 68%. The compound No. of the compound is 3.

Example 4 N- (1-phenyl-2-methyl) propylidene-2 '
-Methoxyethylamine (2.03 g) was dissolved in DMF (20 ml), and bromoacetyl chloride (1.90 g) was gradually added with stirring at room temperature. The reaction solution was added to an oil bath (60
The mixture was heated and stirred in (.degree. C.) for 3 hours. The reaction solution was cooled to room temperature, washed with water, and the organic layer was extracted with ether. 2.31 g of pale yellow viscous liquid was obtained by drying the ether layer with sodium sulfate and then distilling off the ether to purify the viscous liquid obtained by column chromatography (silica gel).
Got

When the infrared absorption spectrum of the compound was measured, it was 3100.
Absorption based on the CH bond in ~2800cm ^-1, amide to 1670 cm ^-1 It showed strong absorption based on.

Moreover, when the mass spectrum was measured, m / e 326,3
28 molecular ion M Peak corresponding to +1, m / e24
6 to M Peaks corresponding to -Br are shown.¹ H-nuclear magnetic resonance spectrum (δ; ppm: tetramethyl
The silane standard, deuterated chloroform solvent) was measured. The solution
The analysis results were as follows.

Its elemental analysis values are C55.18%, H6.23%, N4.28%, and the calculated value C55.25 for the composition formula C ₁₅ H ₂₀ NBrO ₂ (326.24).
It was in good agreement with 23%, H6.18%, N4.29%.

From the above results, the isolated product is N- [1-phenyl-2,
2- (Dimethyl) ethenyl] -N-bromoaceto-2 '
-Methoxyethylamide was found.
The yield was 71%. The compound No. of this compound is set to 4.

Example 5 Various haloacetamide compounds were synthesized by the same method as described in Examples 1 to 4. No., embodiment, physical properties (boiling point or melting point) of the synthesized haloacetamide compound,
Table 1 shows characteristic absorption values in the infrared absorption spectrum (ir) and elemental analysis values. In addition, in the table And Y is And Y.

Next, formulation examples and examples of the herbicidal composition of the present invention will be shown. In the formulation examples and examples, N-substituted-haloacetamide is represented by the compound number [(1) to (56)] in the synthesis example, and the triazine derivative is represented by the symbol [(A) shown in Table 2 below. ~ (I)].

Formulation Example 1 90 parts by weight of compound (E), 6 parts by weight of compound (33), surfactant Solpol 800A [trademark of Toho Chemical Industry Co., Ltd.] 1.5
Parts by weight, surfactant data Gen 60 [lion oil and fat
(Trademark) 1.5 parts by weight and 82 parts by weight of Sieglite were well pulverized and mixed to obtain a wettable powder.

Formulation Example 2 90 parts by weight of compound (F), 6 parts by weight of compound (33), surfactant Solpol SM100 [trademark of Toho Chemical Industry Co., Ltd.] 1
An emulsion was obtained by thoroughly mixing 5 parts by weight and 70 parts by weight of xylene.

Formulation Example 3 Compound (B) 10 parts by weight, Compound (35) 4 parts by weight, Dioctyl succinate 40 parts by weight, Sodium tripolyphosphate 4
By weight, 40 parts by weight of bentonite and 38 parts by weight of talc were thoroughly mixed and pulverized, water was added and kneaded, and then the mixture was granulated and dried, and granulated to 14 to 32 mesh to obtain granules.

Blending Example 4 40 parts by weight of bentonite, 55 parts by weight of talc, and 5 parts by weight of sodium tripolyphosphate are pulverized and mixed, hydrolyzed, kneaded, and then granulated and dried to prepare granules containing no active ingredient. To 85 parts by weight of this granular material, 10 parts by weight of compound (A), compound (3)
Was impregnated with 5 weight% to obtain granules.

Example 1 A Wagner pot equivalent to 1 / 5,000 R was filled with water-mixed paddy soil, and the surface layer of the soil was Novier, Pleurotus cornucopiae,
Broad-leaved weed seeds such as firefly, eel, azalea, sedgeweed, etc. were sown, and tubers of Urikawa and Cyperus japonicus were embedded. 2.5-leaf stage rice seedlings (cultivar name: Akinishi)
Was planted in a depth of 2 cm with 3 plants per plant. After that, the water was applied to the wettable powder prepared according to Formulation Example 1 7 days after transplanting the rice (when Nobie was about 1 leaf stage) under a watering condition of about 3 cm and growing in a glass room at 20 to 25 ° C. And diluted with a predetermined amount.
After that, it was grown in a glass chamber, and 21 days after the treatment with the chemical, the herbicidal effect and the phytotoxicity on the paddy rice were investigated. The results are shown in Table 3.

Herbicidal effect Damage to paddy rice Rice control rate (%) −: Normal 5: 100 (complete withering) ±: Minor damage 4:75 to 99 +: Minor damage 3:50 to 74 ++: Medium damage 2:25 to 49 1: 1 ~ 240: 0 (no effect is observed) Example 2 A 1/8850 arele porcelain pot was filled with upland soil (clay loam soil), various plant seeds were sown to a depth of 0.5 to 1 cm, and then each compound prepared according to Formulation Example 1 or 2 was used. A predetermined amount of a water-dilutable solution of a wettable powder was spray-treated on the soil surface. After the treatment, the plants were grown in a greenhouse at an average temperature of 25 ° C., and two weeks later, the herbicidal effect of each test compound was investigated. The survey results are shown in Table 4. The criteria of the herbicidal effect in Table 4 are the same as in Example 1.

The synergistic effect of the combination of the haloacetamide compound, which is the active ingredient according to the present invention, and the triazine derivative is S. R.
The method proposed by Colby (Weeds, Vol. 15, pp. 20-22)
Further clarify by. The method is to analyze by taking the ratio of the growth rate of weeds to the untreated plot as a measure of the treatment effect of the herbicide.

That is, the measured value of the herbicidal rate when the herbicide S was solely treated with a (g / 10a) was Qa (%), and the herbicidal rate of the herbicide T was solely treated with b (g / 10a). When the measured value is Qb (%), the expected value Qe (%) of the weeding rate when the herbicide S is treated as a mixture with a (g / 10a) and the herbicide T with b (g / 10a) Is The expected value Qe and the measured value Qo (%) are compared with each other, and it can be said that the herbicidal activity by the combination shows a synergistic effect when the Qe value is larger than the Qo value. The synergistic effect of the herbicidal effect between the haloacetamide compound as an active ingredient and the triazine derivative was examined with reference to the results obtained in Example 2 by the above method, and the results are shown in Table 5. It was confirmed from Table 5 that the herbicidal composition of the present invention shows a remarkable excellent herbicidal activity which cannot be obtained by each herbicidal agent due to a large synergistic effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location (A01N 43/70 37:26)

Claims (1)

[Claims] 1. A general formula [However, X represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a phenoxy group, and R ¹ and R ²
Represents the same or different hydrogen atom or an alkyl group, and R ³ represents an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, or a phenyl group (in this case, an alkyl group, an alkenyl group, an alkoxy group and a halogen). Y may be a chlorine atom or a bromine atom. ] An N-substituted-haloacetamide compound represented by (However, Z represents a chlorine atom or an alkylthio group.
R ⁴ and R ⁵ are the same or different alkyl groups and may have a cyano group as a substituent. ) A triazine derivative represented by the formula (3) as an active ingredient.