JPS61134302A - Herbicide composition - Google Patents

Abstract

PURPOSE:To provide a herbicide composition containing a mixture of an N- substituted chloroacetanilide and starch, and exhibiting stable herbicidal effect at a low rate of application by the synergistic effect of the components. CONSTITUTION:The objective composition can be produced by mixing starch to the compound of formula (R1-R3 are H, halogen, alkyl, alkoxy, alkylthio, alkoxyalkyl or alkylthioalkyl; R4 is H or alkyl; R5-R7 are H, halogen, alkyl, alkenyl, alkynyl, alkoxy or alkylthio), e.g. N-[2'-(5'-bromo)-thienylmethyl]-N- chloroaceto-2,6-dimethylanilide, etc., which is a herbicide having broad herbicidal spectrum against perennial weeds such as bulrush, arrowhead, etc. as well as annual weeds in paddy field such as cockspur-grass, monochoria, etc., and capable of effectively controlling the weeds without damaging the paddy rice plant. The amount of starch is 0.5-500pts.wt., (preferably 3.75-320pts. for granule, powder, etc., and 1-32pts. for wettable powder) per 1pt.wt. of the compound of formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a herbicidal composition characterized by mixing starch with N-substituted chloroacetanilide.

[Problem 3 to be solved by the prior art and the invention There are the following four properties that are essentially required of herbicide preparations. That is, one, it must be safe for crops, and two, it must be safe for crops.
Firstly, it should exhibit an even and stable weeding effect against weeds. The third is that the herbicide's effectiveness lasts for a long time.
Fourthly, due to environmental issues, cost, etc., it is necessary to have a more effective herbicidal action with a lower content of active ingredients.

The present inventors conducted extensive research at their own expense to develop a formulation represented by the following general formula as an excellent herbicide.

The following general formula (r), (wherein RI, Rz and R3 represent the same or different hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, alkoxyalkyl group or alkylthioalkyl group, and R4 is Represents a hydrogen atom or an alkyl group, R,,R.

and R1 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups. ) has already been proposed (patent application 1982-
No. 111077 and others. Naturally, the role of formulations in the expression of herbicide effects is very important.

That is, it is almost impossible to expect sufficient herbicidal effects unless the physical or chemical properties of the drug substance are carefully considered and the optimal formulation is formulated.

The present inventors have discovered that the general formula ([N-substituted-
With the aim of using chloroacetanilide more effectively as a herbicide, we have continued intensive research on its formulation, and have found that N
The herbicidal composition obtained by mixing starch with -substituted-chloroacetanilide exhibits a synergistic effect that could not be expected from the properties of each component alone, that is, stable herbicidal effects at low dosages. I discovered something. Based on these new findings, the present inventors have completed and proposed the present invention.

[Means for solving problems]

The present invention is based on the following general formula (1), (wherein R+, 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 R, R6 and R7 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups. N-substituted-chloroacetanilide and starches,
That is, it is a herbicidal composition characterized by mixing one starch selected from starches such as potato, wheat, corn, rice, sweet potato, etc. or a mixture thereof.

A component of the herbicidal composition of the present invention is an N-substituted-chloroacetanilide represented by the following general formula (1).

1, <, i Among the N-substituted-chloroacetanilides represented by the general formula c, the 2-position of the thiophene ring is an alkyl group, R, R, and R4 are hydrogen atoms, and R2 is an alkyl group. , R is also a hydrogen atom, an alkyl group, or an alkoxy group, and R7 is a hydrogen atom, an alkyl group, or a halogen atom, as described in U.S. Patent No. 3901917
It is known by the No. However, most of the others are new compounds.

In the general formula (1), R+, Rz, Rs, Rs,
Specific examples of the halogen atoms represented by R and R1 include chlorine, bromine, fluorine, and iodine atoms.

Furthermore, in the general formula, R1, R1, R3, R4, Rs
, Rh 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-propyl group, n-butyl group, 1so-butyl group, methyl group, n-pentyl group, n-hexyl group. etc. In the general formula (I), R,, R,, R,, R5, R,
The alkoxy group represented by and R7 is not particularly limited, but generally a linear or branched saturated or unsaturated group having 1 to 6 carbon atoms is suitable. Specific examples of the alkoxy group that are generally preferably used include methoxy group, ethoxy group, n-propoxy group, t-butoxy group,
Examples include n-pentoxy group, n-hexoxy group, and allyloxy group.

In the general formula (1), R+, Rz, R:l, Rs
The alkylthio groups represented by R8 and R7 are not particularly limited and any known alkylthio groups can be used, but in general, linear or branched saturated or unsaturated groups having 1 to 6 carbon atoms are preferred. Specific examples of the alkylthio group that are preferably used include methylthio group, ethylthio group, n-
Examples include propylthio group, L-butylthio group, n-pentylthio group, n-hexylthio group, and allylthio group. In addition, in the general formula, the alkoxyalkyl group represented by R1, R2, and R1 is not particularly limited in the 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 alkoxyalkyl group include methoxymethyl group, methoxyethyl group,
Examples include ethoxymethyl group, n-propoxymethyl group, t-butoxyethyl group, and allyloxyethyl group.

Furthermore, in the general formula, the alkylthioalkyl groups represented by R+, Rz and R3 are not particularly limited in the number of carbon atoms, but are preferably linear or branched saturated or unsaturated groups having 2 to 6 carbon atoms. Specific examples of the alkylthioalkyl group include methylthiomethyl group, methylthioethyl group, ethylthiomethyl group, n-propylthiomethyl group, t-butylthioethyl group, and allylthioethyl group.

Furthermore, in the general formula, the alkenyl groups represented by R8, R, and R7 may be linear or branched, and the number of carbon atoms is not particularly limited. However, from the viewpoint of easy availability of raw materials, the number of carbon atoms is preferably 2 to 4. Specific examples of the alkenyl group include vinyl group, allyl group, 1so-propenyl group, 2-butenyl group, and 3-butenyl group. In addition, in the general formula, the alkynyl group represented by Rs, Rh, and R1 is not particularly limited in the number of carbon atoms, regardless of whether it is linear or branched, but the number of carbon atoms is 2 to 4 as described above. It is preferable that Specific examples of the alkynyl group include an ethynyl group and a 2-propynyl group.

Among the above N-substituted-chloroacetanilides, R1 is the same or different halogen atom, alkoxy group, alkylthio group, alkoxyalkyl group, or alkylthio group,
an alkoxyalkyl group or an alkylthioalkyl group, in which R2 and R3 are the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthio groups,
an alkoxyalkyl group or an alkylthioalkyl group, R4 is a hydrogen atom or an alkyl group, R3, R
5 and R7 are the same or different hydrogen atoms, halogen atoms,
Compounds that are alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups or alkylthio groups: 15g/10a
Even when used at a lower concentration than that, it not only has an excellent weeding effect that completely kills annual weeds such as nobies and perennial weeds such as water cypress, but also at a high concentration of 500g/10a. Since it is completely harmless to rice when used, it is suitably used in the present invention. In particular, at least one of R7-R1 is a substituent other than a hydrogen atom, this substituent is substituted at the ortho position of one CH- bonded to the thiophene ring, R4 is a hydrogen atom, and At least two of R9-R1 are substituents other than hydrogen atoms, and N-substituted chloroacetanilide in which these substituents are substituted at the 2nd and 6th positions of the phenyl group has the stronger above properties, so it is particularly Preferably used.

The structure of the N-substituted-chloroacetanilide represented by the general formula (1) can be confirmed by the following means.

(b) By measuring an infrared absorption spectrum (IR), it is possible to observe an absorption based on a CH bond in the vicinity of 3150-2800 cm-' and a characteristic absorption based on a carbonyl bond of an amide group in the vicinity of 1680-1660 cm-'. I can do it.

(b) Measure the mass spectrum (MS) and calculate each peak observed (generally, the ion mass number m is expressed as the ion charge number e).
By calculating the composition formula corresponding to the value expressed by m/e divided by m/e, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule. In other words, since the general formula (I) (hereinafter abbreviated as M) of the sample subjected to measurement is observed as an intensity ratio according to the isotopic abundance ratio depending on the number of halogen atoms contained in the molecule, It is possible to determine the molecular weight of the compound provided. Furthermore, N- represented by the general formula (I)
Substituted-chloroacetanilide Φ ■ Iteha, M Cl, M -COCHz C1
A characteristic strong peak corresponding to R1 is observed, and the binding mode of the molecule can be known.

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

Hfa) H(bl CR3(d)
H(e)hl That is, a singlet corresponding to 6 protons was observed at 2.0 ppa+, and this can be attributed to the methyl groups (dl) substituted at the 2 and 6 positions of the phenyl group.3.
A singlet corresponding to two protons was observed at 6 ppm, and this can be attributed to the methylene group (HL) in the chloroacetyl group. A singlet corresponding to two protons was observed at 4.75 ppm. , this is a methylene group (C
). A quartet corresponding to two protons was observed at 6.67 ppa+, and this can be attributed to the proton (a), mountain) substituted on the thiophene ring. A multiplet corresponding to three protons was observed at 6.95 to 7.30 ppm, and this can be attributed to the protons (el, [f), and (g) substituted with the phenyl group.゛N-substituted- represented by the above general formula (1)
To summarize the characteristics of 'H-NMR of chloroacetanilide, the methylene proton of the chloroacetyl group appears around 3.6 to 3.8 ppm in the normal doublet line, and R4
When is a hydrogen atom, the methylene proton of the aminomethylene group is a singlet of 4.7 to 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), R
When 4 is an alkyl group, the methine proton of the aminomethine group is 5.7 to 6.7 pp+w, and the thiophene 1
Protons on the vote side tend to show characteristic peaks at 5.8 to 7.4 ppIll, and protons on the benzene side tend to show characteristic peaks at 6.0 to 7.7 ppm.

(d) Carbon, hydrogen, nitrogen, sulfur,
By determining the weight percent of each element and halogen, and subtracting the sum of the recognized weight percent of each element from 100, the weight percent of oxygen can be calculated, and the compositional formula can therefore be determined.

Further, N-substituted-chloroacetanilide includes R+, Rz, R3, R4, Rs, R6 and R? in the general formula (I). Although their properties differ somewhat depending on the type, they are generally pale yellow or yellow viscous liquids or solids 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 compounds include benzene, ether, alcohol, chloroform, carbon tetrachloride, acetonitrile,
It is soluble in common organic solvents such as 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 % formula %) (However, in the formula, R+, R, and R5 represent the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylthioalkoxyalkyl groups, or alkylthioalkyl groups, and R4 represents a hydrogen atom or an alkyl group; RS, R& and R.

represents the same or different hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups. ) and the general formula CIICH2
By reacting with chloroacetyl halide represented by COX (where X represents a halogen atom), the N-substituted-chloroacetanilide represented by the general formula (1) can be obtained.

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

In the reaction between the compound represented by the general formula (m) and chloroacetyl halide, the molar ratio of both compounds may be appropriately determined as necessary, but it is usually the same molar ratio or a slightly excess molar amount of chloroacetyl halide. It is common to use

Further, in the above reaction, hydrogen halide is produced as a by-product. Since this hydrogen halide reacts with the aniline derivative represented by the general formula (III) in the reaction system and causes a decrease in the yield of the product, a hydrogen halide scavenger is usually coexisted in the reaction system. It is preferable. The hydrogen halide scavenger is not particularly limited, and any known one can be used.

Examples of the scavenger that are generally suitably used include trialkylamines such as trimethylamine, triethylamine, and tripropylamine, pyridine, sodium alcoholade, and sodium carbonate.

It is generally preferable to use an organic solvent in the reaction. Examples of solvents that are preferably used include:
Benzene, toluene, xylene, hexane, heptane,
Aliphatic or aromatic hydrocarbons such as petroleum ether, chloroform, methylene chloride, ethylene chloride, or halogenated hydrocarbons; ethers such as diethyl ether, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone; acetonitrile, etc. Nitriles; N,N-dialkylamides such as N,N-dimethylformamide and N,N-jetylformamide; and dimethylsulfoxide.

The order of addition of the raw materials in the reaction is not particularly limited, but generally, the aniline derivative represented by the general formula CIII) is dissolved in a solvent, the mixture is charged into a reactor, and the chloroacetyl halide dissolved in the solvent is added under stirring. Good.

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 IO days, preferably 1 to 40 days.
It is sufficient to choose from the time range. Further, during the reaction, it is preferable to perform stirring.

The method for isolating and purifying the desired product, ie, the N-substituted-chloroacetanilide represented by the general formula CI) from the reaction system, is not particularly limited and any known method can be employed. For example, the reaction solution is cooled or allowed to cool naturally to return to room temperature or near room temperature, the reaction solvent and the remaining hydrogen halide scavenger are distilled off, and the residue is extracted with benzene. In the above operation, the salt and high molecular weight compound produced from the by-produced hydrogen halide and the hydrogen halide scavenger are separated. The benzene layer is dried with a desiccant such as Glauber's salt or calcium chloride, and then benzene is distilled off and the residue is vacuum distilled to obtain the desired product. In addition to isolation and purification by vacuum distillation, it can also be purified by chromatography, or if the product is a solid, by recrystallization from a solvent such as hexane.

As another method for producing the N-substituted-chloroacetanilide represented by the general formula (1), the following method is also preferably employed.

General formula (wherein R+, Rt, 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. and X represents a halogen atom. show.

The N-substituted chloroacetanilide represented by the general formula [■] can also be obtained by reacting it with the chloroacetanilide represented by the formula [2].

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

In addition, the conditions and isolation and purification method for carrying out the reaction are those used in the reaction of the aniline derivative represented by the general formula (I[[) with chloroacetyl halide, as described above. The N-substituted chloroacetanilide represented by the above general formula (1), which can be used under almost the same conditions as above, is effective against annual weeds such as Japanese grasshopper, Japanese grasshopper, etc. that occur in paddy fields, as well as perennial weeds such as firefly and Japanese grasshopper. It is an excellent herbicide that has a wide herbicidal spectrum and can efficiently control paddy rice without causing chemical damage.

The other component of the herbicidal composition of the present invention is starch. The starches are not particularly limited, and known ones can be used as they are.
Used.

Specific examples of commonly preferred starches include starches obtained from potatoes, wheat, corn, rice, sweet potatoes, etc., which may be used alone or in a mixture of different types.

As mentioned above, the herbicidal composition of the present invention has the general formula (T)
In the herbicide composition of the present invention containing N-substituted chloroacetanilide and starch, the N-substituted chloroacetanilide and starch are Excellent herbicidal effects can be obtained in an extremely wide range of usage rates. However, in general, the ratio of N-substituted chloroa to toanilide and the starch by weight are in the range of 1 to 500 times in the case of granules, fine granules, powders, and coarse powders. In the case of wettable powders and flowable agents, it is preferable to add in an amount of 0.5 to 50 times. More preferably, in the case of granules, fine granules, powders, and coarse powders, the weight of starch is 3.75 to 32% based on N-substituted chloroacetanilide.
For wettable powders and flowable agents, it is recommended to add the amount in a range of 1 to 32 times. By the above addition, surprisingly, the herbicidal composition of the present invention exhibits a significantly more stable effect than a composition containing no starch, and furthermore, the herbicidal composition of the present invention exhibits a significantly more stable effect than a composition containing no starch. Even if the content of N-substituted-chloroacetanilide represented by is lowered, the same or higher herbicidal effect will be exhibited.

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

The formulation form of the herbicidal composition of the present invention is not particularly limited, and conventionally known formulation forms can be used. For example, it can be prepared and used in powders, coarse powders, fine granules, granules, wettable powders, and flowable preparations.

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

Examples of solid carriers preferably used in the present invention are as follows. For example, clays represented by kaolinite group, montmorillonite group, attapulgite group, thetalite, etc.; talc, mica, phyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, magnesium diatomaceous earth, lime, apatite , zeolite, silicic anhydride, synthetic calcium silicate, and other inorganic substances;
Plant-based organic substances such as soybean powder, tobacco powder, walnut powder, wheat flour, wood flour, 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, O-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, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, n-hexanol, ethylene Examples include alcohols such as glycol and diethylene glycol; ether alcohols such as ethylene glycol phenyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide; and water.

Furthermore, in the preparation of the formulation in the present invention, conventionally known surfactants are used for the purposes of emulsification, dispersion, wetting, spreading, binding, disintegration control, active ingredient stabilization, flowability improvement, rust prevention, etc. It can be used without any restrictions. As surfactants, nonionic,
Although cationic, anionic and amphoteric ones are used, nonionic and/or anionic ones are usually preferred. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; those obtained by polymerizing and adding ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Polymerization of ethylene oxide to alkyl phenols such as isooctylphenol and nonylphenol; Polymerization of 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,
Dilauryl phosphoric acid is also obtained by polymerizing and adding ethylene oxide to mono- or dialkyl phosphoric acid; ethylene oxide is polymerizing and adding to amines such as dodecylamine and stearic acid amide; higher fatty acid esters of polyhydric alcohols such as sorbitan and ethylene oxide are added to them. 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 lauryl sulfate and oleyl alcohol sulfate amine salts; alkyl sulfones such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulfonate. Acid salts; aryl sulfonates such as sodium isopropylnaphthalene sulfonate, sodium methylenedibisnaphthalene sulfonate, sodium ligninsulfonate, and sodium dodecylbenzenesulfonate; phosphates such as sodium tripolyphosphate; and the like.

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

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

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

The method for preparing the formulation in the present invention is not particularly limited, and conventionally known methods can be used. For example, as a specific method for preparing a wettable powder, 1 part by weight of N-substituted-chloroacetanilide is dissolved in an organic solvent, and a carrier containing a surfactant and starch is 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.

In addition, for example, as a specific method for preparing a powder, N-
5 parts by weight of substituted chloroacetanilide, 30 parts by weight of starch
There is a method of obtaining a powder by pulverizing and mixing 65 parts by weight of clay minerals.

Furthermore, for example, as a specific method for preparing granules, 1. 1 part by weight of N-substituted chloroacetanilide, a surfactant, and water are thoroughly kneaded, and then a carrier containing starch and the surfactant are mixed together. In addition, there is a method of obtaining granules by stirring well, extruding into a predetermined particle size, and drying.

In the herbicidal composition of the present invention, additives other than those mentioned above that are normally used in herbicidal compositions may be added as necessary, as long as they do not significantly impair the herbicidal effect.

〔effect〕

The herbicidal composition of the present invention described above exhibits a herbicidal effect that cannot be expected from the properties of each component alone. That is, the embodiments described below also apply to a herbicide usage mode in which the content of the N-substituted dichloroacetanilide, which is an active ingredient of the herbicide, is reduced by adding starch to a specific N-substituted chloroacetanilide. As shown in Figure 2, it exhibits the same herbicidal effect as the N-substituted chloroacetanilide alone. Furthermore, it is extremely safe for crops.

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

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

N--chloroacetanilide (synthesis example 1) N-[2°-(5′-bromo)-chenylmethyl)-2
,6-cynotylaniline 1,81 g (6,14X
10-3 mole) was dissolved in benzene 40 mA and 0.81 g of triethylamine (7,98X 10-3 mole
le) and placed in ice water. Then 0.83 g of chloroacetyl chloride (7,37X10-'mol
The benzene solution (15 mf) of e) was slowly 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 ml of water, 2N
-Salt M50ml! , followed by 50m of water! ! The benzene layer was dried with anhydrous sodium sulfate. After that, it was purified by column chromatography to obtain 1.13 g of yellow solid.
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 2900cn+-' and a strong absorption based on the carbonyl bond of the amide group at 1670c++-'. Its elemental analysis value is C48,
43%, H, 4.05%, N3.99%, Atte, CI
s HIs N S OB, CI (372,71) calculated values for C 48.20%, H4, 32%,
It was in good agreement with N3.75%.

In addition, when the mass spectrum was measured, there was a peak corresponding to C1, a peak corresponding to m/e293, a peak corresponding to M CHCHHz Cl, m/e1
Each peak corresponding to 43 (100%) is shown.

Furthermore, the 1H-nuclear magnetic resonance spectrum is merely shown as a specific example in the specification.

From the above results, the isolated product is N-[2-(5'-bromo)-thenylmethyl]-N-chloroaceto-2,6-
It became clear that it was dimethylanilide (hereinafter abbreviated as compound (1)). The yield is N-(2'-(5'
-bromo)-chenylmethyl]-2,6-dimethylaniline, 49.5% (3,04%
ole).

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

Furthermore, the general formula in Table 1 is the above general formula (1) Corresponding to, A is A,B is R4, D is of means.

Formulation Example 1 (Granules) 1 part by weight of the compound shown in Table 1 N114, 1 part by weight of dioctyl succinate, 3 parts by weight of sodium ligninsulfonate,
15 parts by weight of bentonite, 40 parts by weight of potato starch,
and 40 parts by weight of talc were thoroughly mixed and pulverized, water was added and kneaded, and the mixture was granulated and dried, and the particles were sized to 14 to 32 mesh sizes.

Formulation Example 2 (Water Dispersible) 10 parts by weight of the compound of IT surface fish 6, 2 parts by weight of polyoxyethylene nonylphenyl ether, 200 parts by weight of wheat starch, 20 parts by weight of fine clay, and 48 parts by weight of Zikrite were milled in a hammer mill. The mixture was ground and mixed to obtain a wettable powder.

Formulation Example 3 (Powder) 5 parts by weight of the compound of Na42 in Table 1, 30 parts by weight of corn starch, 1 part by weight of white carbon, and Clay 6
4 parts by weight were ground and mixed in a hammer mill to obtain a powder.

Formulation Example 4 (Fine Granules) 2 parts by weight of the compound shown in Table 1 11h63, 5 parts by weight of sweet potato starch, 5 parts by weight of rice starch, 87 parts of clay and 1 part of polyvinyl alcohol were thoroughly stirred and mixed, and then 5 parts of water was added. At the same time, it is granulated using a transfer granulator and then dried. 48
~ [Sifted through a sieve of 50 ml to obtain fine granules.

In addition, as for comparative examples that do not contain starches, various clay minerals were used instead of starches, and the same method as in Formulation Example 1.2.3.4 was carried out.

Example 1 A 1/8850 are porcelain pot was filled with paddy soil (alluvial loam) that had been stirred with water, and after sowing wild grass seeds, water was added to make it flooded at 3 c. Nobie is 2.
After growth to the 0-leaf stage, a predetermined amount of 3 kg/10 a of granules of each compound produced according to Formulation Example 1 was treated.

After treatment, the plants were grown in a greenhouse at an average temperature of 25° C., and the herbicidal effects of each test granule were investigated three weeks later. The results are shown in Table 2. However, as a comparative example, the results in the case where no starch was included are also listed in the table.

Regarding the weeding effect, weed suppression rate (100-0%) is 1
It was converted into a numerical value from 0 to 0 and evaluated on the following 10 scale.

to: too% (completely dead) 9: 90-99% 8: 80-89% 7: 70-79% 6: 60-69% 5: 50-59% 4: 40-49% 3: 20-39% 2:lo-19% ■ = 1~9% 0:0% (No effect observed at all.) Example 2 Paddy soil (alluvial loam) prepared by adding water to a 1/8850 are porcelain pot and stirring it. After filling and sowing wildflower seeds, water was added to make it flooded to 3 cIll. After the wildflowers grew to the 2.0 leaf stage, a predetermined amount of the aqueous solution of each compound prepared according to Formulation Example 2 was treated with a 300 g/10a hydrating powder. After treatment, the plants were grown in a greenhouse at an average temperature of 25° C., and the herbicidal effects of each test granule were investigated three weeks later. The results are shown in Table 3. However, in the table, as a comparative example, the results in the case where no starch was included are also listed. The criteria for the herbicidal effect in the table are the same as in Example 1.

Margin below

[Brief explanation of drawings]

FIG. 1 shows a 'T(-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 A herbicidal composition comprising 0.5 to 500 times by weight of starch mixed with N-substituted-chloroacetanilide represented by the following formula.