JPS63166807A - Herbicide composition - Google Patents

Abstract

PURPOSE:To obtain a herbicide composition showing high herbicidal effects by synergistic action with a small amount, having a wide herbicidal spectrum, comprising an N-substituted-haloacetamide compound and a pyrazole derivative as active ingredients. CONSTITUTION:(A) A compound shown by formula I [X is H, halogen, alkyl, alkoxy or phenyl; R<1> and R<2> are H or alkyl; R<3> is alkyl, alkenyl, alkoxyalkyl, alkenyloxyalkyl or (substituted)phenyl; Y is Cl or Br] is combined with (B) a compound shown by formula II (R<8> and R<9> are H or alkyl; R<10> is H, halogen or alkyl; n is 1-4; A is benzyl, phenacyl or phenylsulfonyl which may be substituted, respectively] in a blending ratio of 0.01-50pts.wt., preferably 0.2-20 pts.wt. component B based on 1pt.wt. component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a herbicidal composition characterized by containing N-i-substituted haloacetamide and a pyrazole 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 a more effective herbicidal action when applied in small amounts.

Conventionally, many compounds have been synthesized as chloroacetamide compounds, and certain types are known to be useful as herbicides. For example, in JP-A-58-947,
General formula (where R2 is a hydrogen atom or an alkyl group, R8 is a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxyalkyl group, or a benzyl group, and R1 is a hydrogen atom, an alkyl group, an alkenyl group) , an alkoxy group, or an alkoxyal group, and
X3 are each independently a hydrogen, fluorine, chlorine or bromine atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. ) It has been described that N-(1-alkenyl)-croacetanilide represented by the following is useful as a herbicide.
Regarding compounds in which R6 is a 7-aryl group such as a phenyl group, no examples have been reported due to the difficulty of the manufacturing method.

[Means for solving problems]

The present inventors have been conducting synthetic research on a wide range of extractive compounds with excellent physiological activity for many years. In recent years, we have focused on specific compounds with an enamine structure, especially haloacetylated vinylamine compounds, and have conducted intensive research on their synthesis and physiological activities.We have discovered that certain new haloacetamide compounds have been found in various weeds that grow in rice paddies and fields. It has been found that this compound is an extremely useful compound that has excellent activity against humans even at low concentrations, and has no phytotoxicity to crops or toxicity to humans and livestock.

Furthermore, the herbicidal activity of the haloacetamide compound should be further improved (as a result of repeated research, it was found that a composition containing three specific haloacetamide compounds and a specific pyrazole derivative was completely unexpected from their individual properties). The present inventors have discovered that this herbicidal agent exhibits excellent herbicidal activity, exhibits a high herbicidal effect at a lower dose, and has a wide herbicidal spectrum, and has proposed the present invention.

The present invention is based on the following general formula (1) (where X is a hydrogen atom, a halogen atom, an alkyl group,
Indicates an alkoxy group or phenoxy group, R1 and R
Z represents the same or different hydrogen atom or an alkyl group, R3 represents an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, or a substituted or unsubstituted phenyl group, and Y represents a chlorine atom or a bromine atom. Indicates an atom. ) and an N-substituted-haloacetamide compound represented by the following general formula (n) (where RII and R9 represent the same or different hydrogen atoms or alkyl groups, and R" represents a hydrogen atom, a halogen atom, or an alkyl group. , n represents an integer of 1 to 4, and A represents a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenacyl group, or a substituted or unsubstituted phenylsulfonyl group. This is a herbicidal composition characterized in that it is an active ingredient.

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

RI R2 (X is a hydrogen atom, a halogen atom, an alkyl group,
Indicates an alkoxy group or phenoxy group, R1 and R
2 represents the same or different hydrogen atom or an alkyl group, R3 represents an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, or a substituted or unsubstituted phenyl group, and Y represents a chlorine atom or a bromine atom. Indicates an atom. ) The N-substituted haloacetamide represented by the above general formula is a novel compound synthesized for the first time by the present inventors and whose herbicidal activity has been confirmed.

In the general formula (1), specific examples of the halogen atom represented by X include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. In addition, the alkyl group represented by It is. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and [-butyl group. Further, the alkoxy group represented by X is not particularly limited, but a linear or branched alkoxy group having 1 to 6 carbon atoms is generally preferred. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, and t-butoxy group.

The alkyl groups represented by R1 and R2 in the general formula are not particularly limited, but preferably have 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 R3 in the above general formula, the alkyl groups exemplified above for X can be used without particular limitation. Furthermore, the alkenyl group represented by R3 is not particularly limited, but preferably has 2 to 6 carbon atoms. Specific examples of the alkenyl group include alkenyl groups having positional isomers such as propenyl group, phthynyl group, and pentenyl group. Further, the alkoxyalkyl group represented by R3 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, propoxymethyl group, propoxyethyl group, propoxyprobyl group,
Examples include butoxymethyl group, butoxyethyl group, pentoxyethyl group, and the like. Further, the alkenyloxyalkyl group represented by R3 is not particularly limited, but has 4 to 8 carbon atoms.
It is preferable that Specific examples of the alkenyloxy group include alkenyloxy groups having positional isomers such as propenyloxymethyl group, butenyloxymethyl group, pentenyloxymethyl group, propenyloxyethyl group, and propenyloxypropyl group.

Further, as a substituent for the phenyl group represented by R3, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and an allyl group are suitable. 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. group, methoxyphenyl group, methyl (
Examples include substituted phenyl groups having positional isomers such as methoxy) phenyl group, ethyl (ethoxy) phenyl group, allyl phenyl group, and allyl (methyl) phenyl group.

For example, positional isomers of methylphenyl group include 0-methylphenyl group, m-methylphenyl group, and p-methylphenyl group, and examples of dimethylphenyl group include 2,3-dimethylphenyl group, 2,4-dimethyl Examples include phenyl group, 2.5-dimethylphenyl group, and 2.6-dimethylphenyl group.

The structure of the compound represented by the general formula (1) of the present invention is:
This can be confirmed by the following means.

(b) By measuring the infrared absorption spectrum (IR), it is possible to observe absorption based on CH bonds in the vicinity of 3200 to 2800 cm-' and strong absorption based on the carbonyl group of amide in the vicinity of 1680 to 1650 cm-'. .

(0) By measuring the mass spectrum (ms) and determining the composition formula corresponding to each observed peak (generally the mass number expressed as m/e, which is 1 m of ion molecules divided by the ion charge number e), It is possible to know the molecular weight of the compound subjected to measurement and the bonding state of each atomic group within the molecule. In other words, when a sample subjected to measurement is expressed by a general formula, the molecular ion peak (hereinafter abbreviated as MΦ) is generally expressed as an intensity ratio according to the isotope abundance ratio depending on the number of halogen atoms contained in the molecule. Because it is observed,
The molecular weight of the compound subjected to measurement can be determined.

Furthermore, regarding the compound of the present invention represented by the above general formula, M■-Y.

A characteristic peak corresponding to MΦ-COCII□Y was observed, and the binding mode of the molecule could be known.

(c) By measuring the IH-nuclear magnetic resonance spectrum ('Hnmr), it is possible to know the bonding mode of hydrogen atoms present in the compound of the present invention represented by the above general formula. 'H-nm of the compound represented by the above general formula (r)
As a representative example of r (δ, ppm: based on tetramethylsilane, in deuterated chloroform solvent), 'H-nmr analysis was performed on N-(1-(phenyl)ethynyl]-N-chloroaceto-2',6'-dimethylanilide. The result is the following if1/).

That is, at 2.30 ppm there is a singlet of 6 protons based on the methyl group (dl), at 3.75 ppm there is a singlet of 2 protons based on the chloroacetyl group tel, and at 4.41
ppill and ethynyl group (a) at 4.97 ppm,
Based on (b), there are two singlets of one proton each, ? A multiplet of 8 protons based on the benzene ring was observed at , 1Oppm to 7.60ppm.

(iv) Determine the weight percent of each of carbon, hydrogen, nitrogen, and halogen (and sulfur if it contains sulfur) by elemental analysis, and then subtract the sum of the weight percent of each recognized element from 100 to determine the oxygen content. It is possible to calculate the weight% of
Therefore, the compositional formula of the compound can be determined.

The haloacetamide compound of the present invention has the general formula (7
) The properties vary somewhat depending on the types of X, R', R'', R3 and Y, and the degree of purification, but they are generally colorless to dark brown viscous liquids or solids at room temperature and normal pressure.Specifically, they are described below. The compounds of the present invention are shown in Examples.
It is soluble in general organic solvents such as acetonitrile, dimethylformamide, and dimethyl sulfoxide, but poorly soluble in water.

The method for producing the compound represented by the general formula (1) 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, R1 and R2 represent the same or different hydrogen atoms or an alkyl group, and R3 represents an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, or a substituted or unsubstituted phenyl group. . ) and a haloacetyl compound represented by the general formula % (where Y represents a chlorine atom, a bromine atom, and Zi represents a chlorine atom, a bromine atom, 0CCII.Y). The compound represented by the general formula CI) can be obtained by

The Schiff base compound represented by the general formula (I[r]), which is a raw material for this method, may be obtained by any method. Generally, a corresponding carbonyl compound and an amine compound as shown in the following formula are dehydrated. Obtained by condensation.

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

Since acidic products such as hydrogen halides are produced as by-products in this reaction, it is usually preferable to use an acidic component scavenger during the reaction. The type of scavenger may be appropriately selected depending on the reaction conditions (solvent, temperature, etc.), and examples of the scavenger that are generally suitably used include triethylamine, pyridine, and sodium carbonate.

In the reaction in the present invention, it is generally preferable to coexist an organic solvent. Examples of those preferably used include benzene, toluene, xylene, hexane, petroleum ether, chloroform, methylene chloride, ethyl ether, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, acetonitrile, N,N-dimethylformamide, and hexamethyl phosphor. and dimethyl sulfoxide.

1. In particular, when a basic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, etc. is used as the solvent for the reaction, a scavenger for by-produced hydrogen halide may be used. In many cases, the reaction proceeds easily and the desired haloacetamide compound can be obtained in high yield even without coexistence.
Very suitable.

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 (Ill) may be 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, generally from -20°C to 150°C, preferably from -10°C to 12°C.
It should be selected within the range of 0°C. Although the reaction time varies depending on the raw materials and reaction temperature, it is usually sufficient to select it in the range of 5 minutes to 10 days, preferably 1 hour to 50 hours. Further, it is preferable to stir the reaction mixture during the reaction.

The method for isolating and purifying the target product, ie, the compound represented by the general formula (1), from the reaction system is not particularly limited, and any known method can be employed. For example, after the reaction, the reaction solvent and hydrogen halide scavenger are distilled off, water is added, and the residue is extracted with benzene, ether, chloroform, or the like. Furthermore, the desired product can be obtained by drying the organic layer with a desiccant such as sodium sulfate or calcium chloride, distilling off the solvent, and vacuum distilling the residue. 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 polar solvent such as N,N-dimethylformamide as a reaction solvent, a hydrogen halide scavenger is often unnecessary, and low-boiling substances are distilled off after the reaction is completed. Then, the desired product can be obtained simply by vacuum distillation. Moreover, after the reaction is completed,
Water is added to the reaction solution, followed by extraction with benzene, knee gel, chloroform, etc., the organic layer is dried with a desiccant such as sodium sulfate, the solvent is distilled off, and the residue is subjected to vacuum distillation, chromatography, or It is also possible to obtain the desired product by purification by recrystallization.

The compound represented by the general formula (1,) of the present invention exhibits extremely excellent effects as a herbicide. For example, it exhibits excellent herbicidal effects when treating grass weeds, broad-leaved weeds, and perennial weeds in soil before and after germination. Particularly, it exhibits a remarkable herbicidal effect on grass weeds, and for example, it exhibits an excellent herbicidal effect on weeds, which are highly harmful, not only when they germinate, but also when they grow at the 1.5-leaf stage.

It also exhibits a selective herbicidal effect when used as a herbicide in fields, so it can be applied not only to broad-leaved crops such as soybeans, cotton, and beets, but also to grass crops such as wheat, barley, corn, and upland rice without causing damage. I can do it. Furthermore, it can be used as a herbicide for lawns as well as for paddy fields and fields.

The other component of the herbicidal composition of the present invention has the following general formula (II
) (However, R8 and R9 represent the same or different hydrogen atoms or alkyl groups, R" represents a hydrogen atom, halogen atom, or an alkyl group, n represents an integer of 1 to 4, and A is substituted or unsubstituted.) It is a pyrazole m1 body represented by a substituted benzyl group, a substituted or unsubstituted phenacyl group, or a substituted or unsubstituted phenylsulfonyl group.

In the above general formula (n), the alkyl groups represented by R11, R9 and RIG are not particularly limited, and known ones can be used. Generally, those having 1 to 1 g of carbon atoms are preferred. Specific examples of the most suitable groups include methyl group, ethyl group, n-propyl group, and i-propyl group. Among them, those with a methyl group are preferably used because they have high herbicidal activity. In addition, RIo in the above general formula (II)
Examples of the halogen atom represented by include fluorine, chlorine, bromine, and iodine atoms. Also, the above general formula (n)
Among them, a substituted phenyl group, a substituted phenacyl group represented by A,
As the substituent for the substituted phenylsulfonyl group, the alkyl group and halogen atom specifically shown in the above R''+R' and RIG are most preferable.

Among the pyrazole derivatives represented by the above general formula (II), the compound in which RIo and R9 are methyl groups and R16 is a phenyl group with chlorine atoms substituted at the 2nd and 4th positions is the most effective because it has high herbicidal activity. Preferably used.

As a method for producing the pyrazole derivative represented by the above general formula [■], any known production method may be employed without any restriction.

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

The herbicidal composition of the present invention exhibits excellent herbicidal effects over a wide range of usage ratios of the N-substituted haloacetamide represented by the general formula (I) and the pyrazole derivative represented by the general formula (II). can get. However, the usage ratio of both is
Generally, the amount of the pyrazole derivative is in the range of 0.01 to 50 parts by weight per 1 part by weight of the N-substituted haloacetamide. More preferably, 0.2 parts by weight of the pyrazole derivative is added to 1 part by weight of N-i-substituted haloacetamide.
By setting the amount to 20 parts by weight, the herbicidal effect becomes even more excellent.

When the herbicide composition of the present invention is used against wild grasses sown in paddy field soil, the germination of wild grasses is completely inhibited when treated at a concentration of 0.2 g per 1 are;
Even when treated with 00g, there is no effect at all. Therefore, generally 0.15 to 200 g per are, preferably 0.5
~50g of active ingredient may be used in rice fields.

When the herbicide composition of the present invention is used as a herbicide for field crops, it is effective even when treated before and after weed germination, and is highly effective in soil treatment and foliage treatment.
It is widely useful in fields of various grains, legumes, cotton, vegetables, etc. When the herbicide composition of the present invention is used as a field herbicide, for example, germination is completely inhibited when treated with wild grass or crabgrass at a concentration of 0.5 g per are. Therefore, generally 0.2g to 50g per are
The amount of active ingredient may be 0 g, preferably 1 g to 200 g.

Furthermore, the herbicide composition of the present invention has a high degree of safety for lawns and is highly effective. It is more labor-intensive and economical than the other herbicide application methods, and is extremely useful as a herbicide for lawns.

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, any conventionally known solid carrier can be used without any restriction as an appropriate solid carrier. 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, phosphorous lime Inorganic substances such as , zeolite, silicic anhydride, and synthetic calcium silicate; Vegetable organic substances such as soybean powder, tobacco powder, walnut powder, wheat flour, wood flour, starch, and crystalline cellulose; Coumaron resin, petroleum resin, alkyd resin, Synthetic or natural polymer compounds such as 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; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene; carbon tetrachloride,
Chlorinated hydrocarbons such as chloroform, trichloroethylene, monochlorobenzene, and 0-chlorotoluene; Ethers such as dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, and isophorone;
Esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol.

Alcohols such as n-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 of the present invention, conventionally known surfactants are not used for the purposes of emulsification, dispersion, wetting, mineralization, binding, disintegration control, stabilization of active ingredients, improvement of fluidity, rust prevention, etc. Can be used without restriction. 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 alkylnaphthols such as isooctylphenol and nonylphenol. ; Polymerization and addition of ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Polymerization and addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Addition of ethylene oxide to higher fatty acids such as valmitic acid, stearic acid, and oleic acid. Polymerization addition; stearyl phosphoric acid,
Dilauryl phosphoric acid is also a product obtained by polymerizing and adding ethylene oxide to mono- or dialkyl phosphoric acid; a product 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 Examples include esters of alcohols and polyhydric fatty acids such as dioctyl succinate, which is obtained by polymerization and addition of ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium laurate 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 pyrazole derivative and 1 part by weight of an N-substituted haloacetamide are dissolved in an organic solvent, a surfactant and a carrier are added to the solution, and the mixture is thoroughly ground and mixed. There is a method of obtaining a wettable powder by removing the organic solvent.

For example, as a specific method for preparing an emulsion, 10 parts by weight of a pyrazole derivative, 5 parts by weight of an N-substituted haloacetamide, 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 pyrazole derivative, 1 part by weight of an N-substituted haloacetamide, a surfactant and water are thoroughly kneaded, and then a carrier and a surfactant are added. 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, both the N-substituted haloacetamide and the pyrazole derivative exhibit synergistically superior herbicidal effects compared to when each is used alone. For example, the herbicide of the present invention exhibits a far superior herbicidal effect against perennial weeds in rice fields, such as Cyperus spp. Furthermore, when the herbicide of the present invention is used as a field herbicide or a lawn herbicide, it exerts a much wider herbicidal spectrum over 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 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.

〔Example〕

The herbicide composition of the present invention will be specifically explained below using synthesis examples, formulation examples, and examples, but the present invention is not limited to these examples.

Synthesis Example 1 4.57 g of N-(1-methylbenzylidene)-2',6'-dimethylaniline was dissolved in N,N-dimethylformamide (hereinafter abbreviated as DMF.>25mj!) and stirred at room temperature. However, chloroacetyl chloride 2,48
g DMF 5 mj! The solution was added gradually. After stirring at room temperature for a while, the mixture was heated at 60° C. for 2 hours. After cooling the reaction solution to room temperature, it was washed twice with 100 ml of water, and the organic layer was extracted with 100 tal of sodium. After drying the ether layer with sodium sulfate, the solid obtained by distilling off the ether was recrystallized with a mixed solvent of benzene/hexane to obtain colorless crystals with a melting point of 91 to 92°C.
4g was obtained.

When the infrared absorption spectrum of the compound was measured, it was found that 31
Absorption based on carbon-hydrogen bonds was observed at 00 to 2800 cm-', strong absorption based on the carbonyl bond of the amide group at 1680 cr-', and weak absorption based on carbon-carbon double bonds at 1615 cm-'.

In addition, when the t amount spectrum was measured, the molecular ion peak (MΦ) was at m/e299, and the MΦ-C peak was at n+/e264.
Peak corresponding to 1, MΦ-C0CII□ to 222 to sardine
The peaks corresponding to C1, etc. are shown.

'II-Nuclear magnetic resonance vector (δ; ppm: tetramethylsilane (TMS) standard, deuterated chloroform solvent) was measured. The analysis results were as follows.

C0CII□C1 (C) Its elemental analysis values are C72.08%, 85.98%, H
4.80%, and the composition formula〇+sH+sNCO□(29
Calculated value for C72,11%, H6,05 for 9,80)
%, H4, 67%.

From the above results, it is clear that the isolated product is N-(1-(phenyl)
It became clear that the product was ethynyl]-N-chloroaceto-2',6'-dimethylanilide.

The yield was 71%. Let the compound yin of the compound be 1.

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

When the infrared absorption spectrum of the compound was measured, it was found that 31
Absorption based on carbon-hydrogen bond at 00 to 2800 cm-', strong absorption based on amide carbonyl bond at 1670 cm-', and absorption based on carbon-carbon double bond at 1600 cm-'.

In addition, when we measured the mass spectrum, we found that the molecular ion beak (MΦ) was at m/e281, and the MΦ-CH was at m/e266.
, and a peak corresponding to MΦ-CI at m/e 246.

1H-nuclear magnetic resonance spectrum (δ; pI) m: tetramethylsilane standard, deuterium chloroform solvent) was measured. The analysis results were as follows.

”' C0CII□C1 (Coε=Ta) Its elemental analysis values are C63,83%, H7,21%, N
5.12% and has a compositional formula of Cl5II□. NC720(
281,78) calculated value C63,94%, H7,
15%, in good agreement with H4, 97%.

From the above results, it is clear that the isolated product is N-[1-phenyl-2
,2-(dimethyl)ethynyl]-N-chloroace1--
It became clear that it was 2'-methoxyethylamide. The yield was 67%. Let the compound yin of the compound be 2.

Synthesis Example 3 2.18 g of N(1(p-phenoxyphenyl)-2-methylpropylidene]-2'-methoxyethylamine was dissolved in 20mj+ of DMF, and while stirring at room temperature, 1.03 g of chloroacetyl chloride was dissolved. DMF 5 ml
The solution was added gradually. After stirring at room temperature for a while, the mixture was heated and stirred in an oil bath (50°C) for 2 hours. After cooling the reaction solution to room temperature, it was washed twice with water 1001111, and the organic layer was washed with ether 100+++j? Extracted with. After drying the ether layer with sodium sulfate, 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.
I got it.

When the infrared absorption spectrum of this compound was measured, it was 310
0 to 2800c+n-' showed absorption based on carbon-hydrogen bonds, and 1670c+++-' showed strong absorption based on the carbonyl bond of amide.

In addition, when the fffi spectrum was measured, m/e3
Molecular ion peak (MΦ) at 73, M at m/e358
Peak corresponding to Φ-C1,+, MΦ at m/e 358
A peak corresponding to -Ci, etc. was shown at m/e 223.

A 1H-nuclear magnetic resonance spectrum (δ; ppm: tetramethylsilane standard, deuterium chloroform solvent) was measured. The analysis results were as follows.

Its elemental analysis values are C67.41%, H6.45%, N
3.71%, composition formula C,,+1□, NCI On
Calculated value for (373,87) C67,46%, 8
6.47%, in good agreement with N3.75%.

From the above results, it is clear that the isolated product is N-(1-(p-phenoxyphenyl)-2,2-(dimethyl)ethynyl)-
It became clear that it was N-chloroaceto-2'-methoxyethylamide. The yield was 68%. The compound number of the compound is 3.

Synthesis Example 4 N-(1-phenyl-2-methyl)propylidene-2'
-Methoxyethylamine 2.03 g: IcDMF2
1.90 g of bromoacetyl chloride was gradually added while stirring at room temperature.

The reaction solution was heated and stirred in an oil bath (60° C.) for 3 hours.

The reaction solution was cooled to room temperature, washed with water, and the organic layer was extracted with ether. After drying the ether layer with sodium sulfate,
The viscous liquid obtained by distilling off the ether was purified by column chromatography (silica gel) to obtain 2.31 g of a pale yellow viscous liquid.

When the infrared absorption spectrum of the compound was measured, it was found that 31
00-2800c "1. Absorption based on carbon-hydrogen bonds,
A strong absorption based on the carbonyl bond of the amide was observed at 1670 cm-'.

When the mass spectrum was measured, m/e326.
328, a peak corresponding to the molecular ion M @ +1, m
A peak corresponding to M''-Br was shown at /e 246.

1H-nuclear magnetic resonance spectrum (δ; ppm: tetramethylsilane standard, deuterated chloroform solvent) was measured. The analysis results were as follows.

Its elemental analysis values are C55, 18%, H6, 23%, H
4.28%, and the composition formula is C+511zoNBrOz(
Calculated value C55, 23%, 86.326,24).
18% and H4, 29%.

From the above results, it is clear that the isolated product is N-[1-phenyl]
It became clear that it was -2,2-(dimethyl)ethynyl)-N-bromoaceto-2'-methoxyethylamide. The yield was 71%.

The compound yin of the compound is 4.

Synthesis Example 5 Various haloacetamide compounds were synthesized in the same manner as described in Synthesis Examples 1 to 4. The characteristics, aspects, physical properties (boiling point or melting point), characteristic absorption values in the infrared absorption spectrum (i'), and elemental analysis values of the synthesized haloacetamide compounds are listed in Table 1.

Next, formulation examples and examples of the herbicide composition of the present invention will be shown. In addition, in the formulation examples and examples, N-substituted haloacetamides are represented by compound numbers [(l) to (56)) in the synthesis side, and pyrazole derivatives are represented by the following symbols ([A] to [E]).
]).

Formulation example l 10 parts by weight of compound (A), 5 parts by weight of compound (31),
Surfactant Tsurupol 800A (Toho Chemical Industry Trademark)
A wettable powder was obtained by thoroughly pulverizing and mixing 1.5 parts by weight of the surfactant Data Dientro 0 (Lion Oil ■ Trademark) and 82 parts by weight of Zikrite.

Formulation example 2 10 parts by weight of compound (B), 5 parts by weight of compound (41), surfactant Tsurupol 5M100 (Toho Chemical Industry Trademark)
15 parts by weight and 70 parts by weight of xylene were thoroughly mixed to obtain an emulsion.

Formulation example 3 10 parts by weight of compound (A), 1 part by weight of compound (35),
4 parts by weight of dioctyl succinate, 4 parts by weight of sodium tripolyphosphate, 41 parts by weight of bentonite, and 40 parts by weight of talc.
Parts by weight were thoroughly mixed and pulverized, water was added, kneaded, granulated and dried, and 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. 7 parts by weight of compound (B) was added to 85 parts by weight of this granular material, and compound (B) was added to 85 parts by weight of the granules.
8 weight of 3) was impregnated to obtain granules.

Example 1 A Wagner pot equivalent to 1/5000 are was filled with watered and kneaded paddy soil, and seeds of broad-leaved weeds such as Japanese grasshopper, Japanese cypress, Japanese cypress, and broad-leaved weeds such as Japanese grasshopper, Japanese cypress, and Japanese cypress were sown on the surface layer of the soil. Embedded tubers. Furthermore, three rice seedlings (variety name: Akinishiki) at the 2.5-leaf stage were planted at a depth of 2 cm. Thereafter, the rice was grown in a glass room at 20 to 25°C under warm water conditions of about 3 cm, and 7 days after transplanting (when the wildflowers were at about one leaf stage), a hydrating powder prepared according to Formulation Example 1 was added to the water. It was diluted and a predetermined amount was dropped. After that, they were grown in a glass room, and after being treated with chemicals, they were grown for 21 days.
On day 0, the herbicidal effect and phytotoxicity on paddy rice were investigated.

The results are shown in Table 2.

Weeding effect 0... Weed suppression rate 0-9%1...
・Weed suppression rate 10-29%2 ・・・・・・ Weed suppression rate
30-49%3 ・・・・・・ Weed suppression rate 50-69%
4... Weed suppression rate 70-89%5...
... Weed suppression rate 90-100% Transplanted rice chemical damage - ... Normal ± ... ... Slightly small + ... ... Small + + ... Medium damage according to the present invention S, the synergistic effect of the combination of the active ingredients haloacetamide compound and pyrazole derivative.
The method proposed by R. Colby (Weeds + vol. 15,
20-22). In this method, the percentage ratio of weed growth to the untreated plot is analyzed as a measure of the treatment effect of the herbicide.

That is, the actual value of the herbicide suppression rate when herbicide S was treated alone with a (g/10a) was Qa (%), and the herbicide suppression rate when herbicide T was treated alone with b (g/10a) was Qa (%). When the measured value is Qb (%), the herbicide S is a (g/
10a) and herbicide T (g/1Oa) when treated as a mixture, calculate the expected value Qe (%) of the weed suppression rate using the following formula, and calculate the expected value Qe and the actual value Qo (%). When the Qe value is greater than the Qo value, it can be said that the herbicidal activity of the combination exhibits synergistic action. The synergy of the herbicidal effect between the haloacetamide compound and the pyrazole derivative, which are active ingredients, was investigated by the method described above with reference to the results obtained in Example 1, and the results are shown in Table 3. From Table 3, it was confirmed that the herbicidal composition of the present invention exhibits remarkable herbicidal activity that cannot be obtained with each herbicide alone due to a large synergistic effect.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, X is a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkoxy group or a phenoxy group, R^1 and R^2 represent the same or different hydrogen atoms, or an alkyl group, and R^3 represents an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkenyloxyalkyl group, or It represents a substituted or unsubstituted phenyl group, and Y represents a chlorine atom or a bromine atom. ) and the general formula ▲mathematical formula, chemical formula, table, etc.▼ (However, R^8 and R^9 represent the same or different hydrogen atoms or alkyl groups, and R^ 1^0 represents a hydrogen atom, a halogen atom, or an alkyl group, n represents an integer of 1 to 4, and A represents a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenacyl group, or a substituted or unsubstituted phenacyl group. A herbicidal composition characterized by containing a pyrazole derivative represented by (representing a phenylsulfonyl group) as an active ingredient.