JPS61145105A - Herbicide composition - Google Patents

Abstract

PURPOSE:A herbicide composition showing herbicidal action, having a wide herbicidal spectrum, higher herbicidal effects with the same application amount of each component alone, obtained by blending an N-substituted-chloroacetanilide with benzylurea. CONSTITUTION:(A) A compound shown by the formula I (A is halogen, alkoxy, or alkylthio; R1-R3 are H, halogen, alkyl, alkoxy, or alkylthio), such as N-[2'-(3'-methoxy)-thienylmethyl]-N-chloroaceto-2,6-dimethylanilide, is blended with (B) a compound shown by the formula II (X is halogen, CF3, alkyl, or alkoxy), such as 1-(alpha, alpha-dimethylbenzyl)-3-(2'-chlorobenzyl) urea in a weight ratio of 1pt.wt. component A to 0.01-100pts.wt., preferably 1-10pts.wt. compo nent B. High effects are obtained by soil treatment of foliar treatment before and after germination of weeds and the composition is effective especially as a herbicide for paddy fields.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application) The present invention relates to a herbicide composition effective as a herbicide for paddy fields or field cultivation.

(Technical Problem) Conventionally, conventional compounds or mixtures are known as herbicides. However, there has been a demand for the development of compounds that exhibit good herbicidal activity even when used in small amounts. The present inventors have already proposed several new herbicides having novel herbicidal activity. Furthermore, as a result of research and development of herbicides with excellent herbicidal activity, we found that by mixing specific compounds, we not only have superior herbicidal activity compared to each compound alone, but also kill many weeds with a very small amount of active ingredient. We have confirmed that it can eliminate weeds and have come to propose it here.

(Solution Means) The present invention provides the following: (i) General formula % Formula % (However, the person in the formula is a halodane atom, an alkoxy group, t
R4, R2 and R5 each represent the same or different hydrogen atom, halodane atom, or alkyl group. Indicates an alkoxy group or an alkylthio group. ) and N-substituted-chloroacetanilide represented by (iD
This is an unveiling agent composition mixed with dibenzylurea represented by the general formula (wherein, X represents a halodane atom, a trifluoromethyl group, an alkyl group, or an alkoxy group).

One of the herbicide components of the present invention has the general formula (however, the person in the formula is a halodane atom, an alkoxy group, t
or an alkylthio group, and R,, R2 and R3 each represent the same or different hydrogen atom, dihalon atom, alkyl group, alkoxy group, or alkylthio group. ) is an N-substituted chloroacetanilide.

A specific example of the halodane atom represented by A, R1, R2 and R5 in the above general formula (i) of the present invention is chlorine.

Examples include bromine, fluorine, chlorine, and iodine atoms. In the above general formula, the alkoxy groups represented by A, R1, R2 and R3 are not particularly limited, but generally have 1 to 6 carbon atoms.
Straight-chain or branched saturated to unsaturated groups are preferred. Specific examples of the alkoxy group that are generally preferably used include methoxy group, ethoxy group, n-propoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, allyloxy group, and the like. In the general formula (i) of the present invention, the alkylthio groups represented by A, R,, R2 and R5 are not particularly limited and any known alkylthio group can be used, but generally a straight chain group having 1 to 6 carbon atoms is used. Preferred are saturated or unsaturated radicals in the form of or branched. Specific examples of the alkylthio group that are preferably used include:
Methylthio group, ethylthio group, n-propylthio group.

Examples include t-butylthio group, n-pentylthio in-hexylthio group, and allylthio group. Furthermore, the alkyl groups represented by R4, R2, and R3 in the general formula (i) are not particularly limited and any known alkyl group can be used, but generally a straight chain or branched alkyl group having 1 to 6 carbon atoms is used. Saturated or unsaturated groups are preferred. Specific examples of the alkyl group that are generally preferably used include methyl group, ethyl group, n-propyl group + 1so-propyl group, and n-butyl group.

1so-butyl group, t-butyl group, n--en ethyl group.

Examples include n-hexyl group, allyl group, and ethynyl group.

The compound represented by the general formula (i) of the present invention is a novel compound, and its structure can be confirmed by the following means.

(b) By measuring the infrared absorption spectrum (IR), it is possible to observe an absorption based on the CH bond in the vicinity of 3150 to B8003-', and a characteristic absorption based on the carkenyl bond of the amide group in the vicinity of 1680 to 1670m. I can do it.

(b) Measuring the mass spectrum (ms) and calculating a composition formula that corresponds to each observed peak (generally a value expressed as rrV'-, which is the ion mass number m divided by the ion charge number e) From K, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule. In other words, when a sample subjected to measurement is expressed by the general formula C0CH2Ct, the molecular ion peak (hereinafter abbreviated as Me) generally follows the isotope abundance ratio depending on the number of Nologon atoms contained in the molecule. The molecular weight of the compound subjected to measurement can be determined because it is observed by the intensity ratio. Furthermore, regarding the compound of the present invention represented by the above general formula, Me-CA.

A characteristic strong bond corresponding to Me-COCH2Ct and A9°H2CK was observed, and the binding mode of the molecule could be known.

(c)/H-nuclear magnetic resonance spectrum ('H-nmr)
By measuring K, 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-n of the compound represented by the general formula (i)
As a representative example of mr ('eppln: in 9-fold chloroform solvent based on tetramethylsilane), N-(2'-(
The 'H-nmr diagram of 5'-f rom)-thenylmethyl-N-chloroaceto-2,6-dimethylanilide is shown in FIG. The analysis results are as follows.

(h) That is, a singlet corresponding to 6 protons was observed at 2.0 ppm, and can be attributed to methyl groups (φ) substituted at the 2 and 6 positions of the phenyl group.

A singlet corresponding to two protons was observed at 3.66 ppm, and can be attributed to the methylene group (h) in the chloroacetyl group. A singlet corresponding to two protons was observed at 4.75 ppm, and can be attributed to the methylene group (C). Protons at 6.67ppm
A quartet corresponding to two frogs is observed, and can be attributed to protons (a) and (b) substituted on the thiophene ring. 3 protons at 6.95-7.30 ppm
Multiplets corresponding to individual components were observed and attributed to protons (@), (f), and (g) substituted with phenyl groups.

To summarize the 'H-nmr characteristics of the compound represented by the above general formula (i), the methylene proton of the chloroacetyl group is usually a singlet around 3.6 to 3.8 ppm.

The methylene proton of the aminomethylene group is a single line at around 4.8 ppm (however, if there is an asymmetric substituent at the 2.6 position on the aniline side, it may appear as a double line). , the proton on the thiophene ring side is 5.8~
At 7.4 ppm (however, at the 5th position of the thiophene ring), the proton on the benzene side calculates the weight percent of each of the 6.0 to rogons, and further subtracts the sum of the weight percent of each recognized element from 100. Therefore, the weight percent of oxygen can be calculated, and the compositional formula of the compound can therefore be determined.

The N-substituted-(2-chenylmethyl)-N-chloroacetanilide of the present invention is A in the general formula.

Although their properties differ somewhat depending on the type of R1, R2, and R3, they are generally pale yellow or yellow viscous liquids or solids at normal temperature and pressure, and many have extremely high boiling points. As will be specifically shown in the examples below, the boiling point of the above compound tends to increase as the molecular weight increases, like general organic compounds. Compounds of the present invention include benzene and ether.

It is soluble in common organic solvents such as alcohol, chloroform, carbon tetrachloride, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide, but almost insoluble in water.

The method for producing the compound represented by the general formula (i) of the present invention is not particularly limited. Specific examples will be described in detail in the synthesis examples described below, but a typical manufacturing method will be described as follows. General formula (where A) represents a rhodane atom, an alkoxy group, or an alkylthio group, and R1r R2 and R3 each represent the same or different hydrogen atom, halodane atom, alkyl group, alkoxy group, or alkylthio group. ) and a compound represented by the general formula C1CH2-coy (however,
Y represents a halodane atom. ) The compound represented by the general formula (i) can be obtained by reacting with the chloroacetyl halide represented by the above formula (i).

The a=+7one derivative represented by the general formula (2) as a raw material can be obtained by any method.

In the reaction between the compound represented by the general formula (2) and chloroacetylhalodanide, the molar ratio of both compounds may be appropriately determined as necessary, but it is usually equal molar or slightly smaller than chloroacetylhalonide. It is common to use a molar excess.

Further, in the above reaction, hydrogen halide is produced as a by-product. This hydrogen halide reacts with the compound represented by the general formula (2) in the reaction system, causing a decrease in the yield of the product, so a hydrogen scavenger is usually coexisted in the reaction system. It is preferable to let

The hydrogen halide scavenger is not particularly limited, and any known one can be used. Examples of the scavenger that are generally suitably used include trialkylamines such as trimethylamine, triethylamine, and tripropylamine; pyridine; sodium alcoholade; and sodium carbonate.

In the reaction in the present invention, it is generally preferable to use an organic solvent. Examples of solvents suitably used include benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, [aliphatic or aromatic hydrocarbons such as ethylene chloride, or] rhodane. Hydrocarbons; Ethers such as zoethyl ether, dioxane, and tetrahydrofuran;
Ketones such as acetone and methyl ethyl ketone; nitrites such as acetonitrile; N,N-dialkylamides such as N,N-dimethylformamide and N,N-diethylformamide; dimethylsulfoxide and the like.

The order of addition of raw materials in the reaction is not particularly limited, but generally, the compound represented by the general formula (2) is dissolved in a solvent, the reactor is charged, and the chloroacetyl halonide dissolved in the solvent is added under stirring. It is better to do so. 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 reaction can be selected from a wide range, and generally it is sufficient to select it from the range of -20°C to 150°C, preferably 0°C to 120°C. The reaction time varies depending on the type of raw material, but is usually 5 minutes to 10 days, preferably 1 to 4 days.
It is sufficient to select from the range of 0 hours. It is also 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 (i), 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 rhodanide scavenger are distilled off, and the residue is extracted with benzene. In the above operation, salts and high molecular weight compounds generated from the by-produced hydrogen rodanide and the hydrogen rodanide 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.

Furthermore, the general formula (where Am represents a halodane atom, an alkoxy group, or an alkylthio group, and Y represents a lodene atom). ) and the general formula (where R, R and R3
represents the same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, and alkylthio groups. ) The compound represented by general formula (i) can also be obtained by reacting with chloroacetanilide represented by formula (i).

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

In addition, the conditions and isolation and purification method for carrying out this reaction are almost the same as those used in the reaction of the compound represented by general formula (2) and chloroacetyl halonide as described above. Similar conditions can be adopted.

Another component constituting the herbicidal composition of the present invention is a dipenzolurea represented by the general formula: (wherein, X represents a halodane atom, a trifluoromethyl group, an alkyl group, or an alkoxy group). When X is a halodane atom in the dibensol urea represented by the above general formula (3), chlorine, bromine,
Halodane atoms of iodine and fluorine are used, but in terms of herbicidal effect, fluorine atoms may be a little more powerful than other halodanes. In addition, X in the general formula (3)
When is an alkyl group or a haalkoxy group, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc., is preferably used as the alkyl group.

The compound represented by the above general formula (3) can be synthesized by reacting incyanate and an amine, for example, as shown in the following formula.

In formula C, X has the same meaning as above. ) These reactions can be performed without solvent or with benzene or toluene.

1 at room temperature to 50°C in the presence or absence of a basic catalyst in an organic solvent such as xylene, acetone, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, pyrison, zomethylformamide, methanol, or ethanol. This is done by stirring or standing for ~5 hours. After the reaction is completed, the target compound is separated from the reaction mixture according to a conventional method.

N-substituted chloroacetanilide represented by the general formula (i), which is a constituent active ingredient of the herbicidal composition of the present invention;
Excellent herbicidal effects can be obtained in a wide range of ratios of use with zopendylurea represented by the general formula (3). However, the ratio of the two used is generally in the range of 0.01 to 100 parts by weight, preferably 1 to 20 parts by weight, of nopennorurea per 1 part by weight of N-substituted chloroacetanilide.

The herbicidal composition of the present invention, which is a mixture of the compounds represented by the above general formulas (i) and (3), has a slight difference in herbicidal effect depending on the difference in the functional groups, but has little phytotoxicity against grass crops. A common characteristic is that they have little phytotoxicity, especially to paddy rice. Examples of weeds on which the compound of the present invention exhibits herbicidal effects are as follows.

As mentioned above, it has a high herbicidal effect on grass weeds, the common grass weed, and it also has a remarkable herbicidal effect on Cyperaceae, especially Cyperus cyperus, Cyperus japonica, Firefly, etc. Next to these, it has a herbicidal effect on broad-leaved weeds. Weeds that can be particularly effectively weeded are, for example, golden weed, brown weed, canine pie, staghorn weed, Tama ga yari, water lily, Hina ga yari, Japanese grass moth, firefly, harrier, and staghorn grass.

Himetentuki, Hideriko, Japanese cypress, Japanese cypress, Japanese black guinea pig, Japanese pine flycatcher, Japanese cypress, black-and-white chickadee, white-breasted buttercup, silver-eared pear, white-breasted buttercup, silver lily, Japanese cypress, Japanese parsley, Japanese parsley, willow knotweed, and Japanese cypress.

Ibokusa, Hoshikusa, Japanese chickweed, and Japanese chickweed.

These are paddy field weeds such as Kikashigusa, Mizumappa, Himeson, Chozotade, Azemushiro, Takasaburo, Taukogi, American Meliflower, Scutellaria japonica, Sawtougara, Japanese horsetail, Japanese azalea, and Azetogonium. Also, field weeds include, for example, crabgrass.

Green foxtail, pigweed, Japanese knotweed, and cyperus.

It can be applied to small-sized snails, common grass, purslane, red-breasted grass, oxalis, sycamore, sycamore, Japanese violet, black-and-white violet, Japanese violet, Japanese pea, shepherd's purse, etc.

The herbicide composition of the present invention can be used as a herbicide for paddy fields or as a herbicide for field cultivation without particular limitation. Particularly effective are herbicides for paddy fields. Typical embodiments of using the herbicide composition of the present invention as a herbicide are explained below.

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

Therefore, generally 0.15 to 200. p, preferably 0.5 to 509 p, may be used in paddy fields.

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

The herbicidal composition of the present invention may be sprayed as a raw material itself, or may be sprayed as a preparation prepared by mixing it with a carrier and, if necessary, other adjuvants. The formulation form is not particularly limited, and conventionally known formulation forms can be used. For example, powder
It can be prepared and used in coarse powders, fine granules, granules, wettable powders, emulsions, flowable preparations, oil suspensions, etc.

When preparing the herbicidal composition of the present invention into a formulation, conventionally known solid carriers can be used without any limitations as suitable solid carriers. Examples of solid carriers preferably used in the present invention are as follows. For example, clays represented by kaolinite group, montmorillonite group, atta/arugite group, ziecrite, etc.; talc, mica,
phyllite, pumice, miculite, gypsum, calcium carbonate, dolomite, ke-1 soil, magnesium,
Inorganic substances such as lime, apatite, zeolite, anhydrous silicic acid, 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 Synthetic or natural polymer compounds such as resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, corn rubber, and dammar rubber; waxes such as carnauba wax and beeswax; urea, etc. can be mentioned.

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. Rough-in or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, etc.
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 keto/, diisobutyl ketone, cyclohexanone, acetophenone, and inphorone;
Esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, tubyl maleate, diethyl succinate; methanol,
n-hexanol, ethylene glycol, diethyl 7
f 17 :Alcohols such as 1-ru; ether alcohols such as ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide, or water.

In addition, the preparation of the formulation in the present invention includes emulsification.

Conventionally known surfactants can be used without any restriction for purposes such as dispersion, wetting, spreading, binding, disintegration control, active ingredient stabilization, fluidity improvement, and rust prevention. As the surfactant, nonionic, cationic, anionic and amphoteric surfactants can be used, and usually nonionic and/or anionic surfactants are preferably used. Suitable nonionic surfactants include, for example, lauryl alcohol, stearyl alcohol, oleyl alcohol, higher alcohols with ethylene oxide polymerized, and alkylphenols such as octylphenol and nonylphenol with ethylene oxide polymerized; butyl. Products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as naphthol and octylnaphthol; - Products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as lumitic acid, stearic acid, and oleic acid; Stearic acid, dilauryl phosphoric acid, mono- Or a product obtained by polymerizing and adding ethylene oxide to dialkyl phosphoric acid;
Products obtained by polymerizing and adding ethylene oxide to amines such as dodecylamine and stearic acid amide; Products obtained by polymerizing and adding ethylene oxide to higher fatty acid esters of polyhydric alcohols such as sorbitan; Products obtained by polymerizing and adding ethylene oxide and propylene oxide; Dioctyl Examples include esters of polyhydric fatty acids such as succinate and alcohols. Suitable anionic surfactants include:

For example, sodium lauryl sulfate, oleyl alcohol sulfate ester amine salt, alkyl sulfate salt; sodium sulfosuccinate dioctyl ester, 2
- Alkyl sulfonates such as sodium ethylhexene sulfonate; sodium inpropylnaphthalene sulfonate, sodium methylene bisnaphthalene sulfonate,
Aryl sulfonates such as sodium lidanine sulfonate 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, to enhance the herbicidal effect by improving properties such as disintegration of granules.

Examples of adjuvants preferably used in the present invention are as follows.

Casein, gelatin, albumin, glue, sodium alginate, cal? Examples include polymer compounds such as oxymethylcellulose, methylcellulose, hydroxyethylcellulose, 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 an irrigation agent, 10 parts by weight of dibenzylurea and 1 part by weight of N-substituted-chloroacetanilide are used.
There is a method of obtaining an irrigation agent by dissolving part by weight in an organic solvent, adding a surfactant and a carrier to the solution, pulverizing and mixing well, and then removing the organic solvent.

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

Furthermore, as a specific method for preparing granules, for example, 10 parts by weight of di(dilurea, 1 part by weight of N-substituted-chloroacetanilide, a surfactant and water are thoroughly kneaded, and then a carrier and a surfactant are mixed together. After adding the agent and stirring well,
There is a method of obtaining granules by extruding to a predetermined particle size and drying.

〔effect〕

The herbicidal composition of the present invention described above exhibits a herbicidal effect that cannot be expected from the properties of each component alone. That is, the herbicidal composition of the present invention exhibits a synergistic medicinal effect compared to the herbicidal effect of both N-substituted-chloroacetanilide and dibenzylurea when used alone. Therefore,
The herbicidal composition of the present invention has a broader herbicidal spectrum than that of its constituent components alone. moreover,
It has a greater herbicidal effect at the same level as the application amount of each component alone. Moreover, it is safe for crops.

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

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

Synthesis Example I N-(2'-(3'-methoxy)-thenylmethyl]-2,6-dimethylaniline 5.8111 (0,0
24 mol) was dissolved in 40 ml of benzene, 3.10 I CO 1 mol of triethylamine was added, and the mixture was placed in ice water. Then chloroacetyl chloride 3.19
,! i+ (0,028mot・) in benzene solution (
i5m) was added gradually. After stirring for 3 hours, 50℃
It was heated for 3 hours.

After the reaction mixture was cooled to room temperature, it was washed successively with 50 ml of water, 50 ml of hydrochloric acid, and then 50 ml of water, and the benzene layer was dried over anhydrous sulfuric acid. After distilling off benzene under reduced pressure, the residue was vacuum distilled to a boiling point of 172°C.
5.03 g of pale yellow solid with 70.15 mHg was obtained. The results of measuring the infrared spectrum of this product are shown in Figure 2. It shows a strong absorption based on the C-H bond at 3100 to 2800α, and a strong to strong absorption based on the cargenyl bond of the amide group at 1670crR-'. Ta.

Its elemental analysis values are C59, 20%, ) 15.64%.

N4.37%, composition formula C46H18NSO2C
C59.33, which is the calculated value for t(323,84)
%.

There was good agreement with H5, 61% and N4.33ch.

Also, when we measured the mass spectrum, w′e323
The molecular ion peak corresponding to the molecular weight, Me.

A peak corresponding to Me-ct at rry'e 288,
The peak corresponding to Me-COCH2C4 is at n1/e 246, and the peak corresponding to Me-COCH2C4 is at m/e127.Furthermore, the 'H-nuclear magnetic resonance spectrometer (δ; ppm: monochloroform solvent based on tetramethylsilane) is measured. The results are shown in Figure 3. Indicated. The analysis results are as follows.

A single line corresponding to 6 protons is shown at 1.95 ppm, which corresponds to the methyl protons in (f) substituted at the 2 and 6 positions of the phenyl group. A single line for three protons is shown at 3.50 ppm, which corresponds to the methyl proton in (a).

A single line for two protons is shown at 3.72 ppm, (
, ) corresponds to the methylene proton. 4゜75 ppm
shows a single line for two protons, which corresponds to the methylene proton in (d). A quartet of two protons is shown at 6.55 ppm, which corresponds to the protons of the thiophene rings in (b) and (c). A multiplet of three protons is shown at 7.00-7.45 ppm, and (ω, (h), and (i
) corresponds to the proton of the benzene ring.

From the above results, it can be seen that the isolated product is N -C2/ -(3/
-methoxy)~thenylmethylcou N-chloroace)-
It became clear that it was 2,6-dimethylanilide. The yield was 66.2 for N-C2'-C3'-methoxy)-thenylmethyl)-2,6-tumethylaniline.
96 (0,016 mole).

Synthesis example 2 2.6-danityl-N-chloroacetanilide 2.71
9 (0,012mole), 2-chloromethyl-
5-Ethoxythiophene 2.12. li' (0,01
2 mole) and potassium carbonate 0.83,! i' (6
, OX 10-3 mole) was added to N,N-methylformamide (hereinafter abbreviated as DMF) 5 (laj) and stirred. The reaction mixture was heated at 100°C for 3 hours, and then stirred at room temperature for 1 hour. did.

After filtering off the precipitated potassium chloride, DMF in the filtrate was distilled off under reduced pressure, 100M water was added to the residue, and the mixture was extracted with ether. After drying the ether layer over anhydrous sulfuric acid (IJum), the ether was distilled off under reduced pressure. The residue was vacuum distilled to obtain 3.50 g of a yellow viscous liquid with a boiling point of 182° C. and 10.30 Hg. When the infrared spectrum of this product was measured, it showed an absorption based on a C-H bond at 3100 to 2800 cm-1, and a strong absorption based on a cargenyl bond of the amide group at 1670 cm-'. Its elemental analysis values are C62.21% and H6.61%.

N3.90%, composition formula C1, H24NSO2C
C62.36 which is the calculated value for L(365,92)
blood .

It was in good agreement with H6, 62% and N3.84ch.

In addition, when we measured the mass spectrum, we found that rrv'03
65 is the molecular ion peak corresponding to the molecular weight.

M"', peak corresponding to MO-Ct at rrV/@330.

Peak corresponding to MO-C0CH2CLK at Iv/@288, H5C20QC at rrV/e141 (i00%)
Each peak corresponding to H2e is shown.

Furthermore, 'H-Nuclear Magnetic Resonance Coverage (a: ppm
: tetramethylsilane standard double chloroform solvent) The results are shown in FIG. The analysis result is as follows.

C0CH2CL (f) 1,15 A triplet line for 6 protons is shown in PP'ZI, which corresponds to the methyl proton in (h) of the ethyl group substituted at the 2.6-position of the phenyl group. A triplet line corresponding to three protons is shown at 1.40 ppm, which corresponds to the methyl proton in (a) of the ethoxy group substituted on the thiophene ring.

A quartet of four protons is shown at 2.39 ppm, which corresponds to the methylene proton in (g) of the ethyl group substituted at the 2.6-position of the phenyl group. A single line for two protons is shown at 3.66 ppm, which corresponds to the methylene proton in (f). 4. (b) shows a quartet of two protons at O4ppm, and shows an ethoxy group substituted on the thiophene ring. )
-y-77f. , corresponds to 7. 4.75ppmK de
Two single lines of 10 tons are shown and correspond to the (@) methylene proton adjacent to the thiophene ring. 5.9
A doublet corresponding to 71 protons is shown at 5 ppm, which corresponds to the proton (c) on the thiophene ring. 6.39 ppm
shows a doublet for one proton, and (
Corresponds to the proton in d). 7.10-7.40pp
mK multiplets are shown, (i), (j), and (h)
corresponds to the proton of the benzene ring.

From the above results, it is clear that the isolated product is N-[2'-(5'-ethoxy)-fenylmethyl]-N-chloroaceto-2,
It became clear that it was 6-diethylanilide. The yield was 79.7 moles based on 2,6-diethyl-N-chloroacetanilide.

Synthesis Example 3 N -(2'-(3'-methoxy) in Synthesis Example IK
-2,6--) N-[2'-(3'-chloro)-chenylmethyl]-2-methyl-6-itudelopylaniline 2.14 instead of methylaniline
9 (7,66X10-5 mole) was used.
The reaction was carried out in the same manner as in Synthesis Example 1, and the post-treatment was carried out, and the boiling point was 167°C.
/ 0.15 taps Hg pale yellow solid 1.08,
I got a 9.

As a result of measuring the infrared spectrum of this product, it was found that 3120 ~
Absorption based on C-H bond at 2900 cm-'.

It showed strong absorption at 1675tM-1 due to the carmenyl bond of the amide group. Its elemental analysis value is C57.47%.

1 (5,47%, ~4.03%, composition formula C1,
It was in good agreement with the calculated values of C57.30%, H5,39ch, and N3.93ch for Hl, N5OC42 (356,31).

In addition, when the mass spectrum was measured, a molecular ion peak corresponding to the molecular weight was found at φ355.

Peak corresponding to M''-CLK at MO, rry'e 320.

Peak corresponding to Me-C0CH2CL at rV/@277.

Furthermore, the /a-nuclear magnetic resonance spectrum (δ; ppm: monochloroform solvent based on tetramethylsilane) was measured, and the results are shown in FIG. The analysis results are as follows.

COCH2C1 (d) Shows a quartet of 6 protons at 1.13 ppm, and shows two (
Corresponds to the methyl proton of f). 1.92 ppmK
A single line for three protons is shown and corresponds to the methyl proton in (e) substituted at the 6-position of the phenyl group.

2.80 pprnK Shows the multiplet of one proton,
It corresponds to the methyl proton in (i) of the isopropyl group.

A single line for two protons is shown at 3,74 pprn,
(d)) = 16 Hz), which corresponds to the methylene proton in (c) adjacent to the thiophene ring. 6.66-7.
Showing the multiplet of two protons at 10 ppm,
This corresponds to the two protons (a) and (b) of the thiophene ring.

7, 10-7.35 ppmK Shows multiplets of three protons, (f), (g), (h) of phenyl group
This corresponds to three protons.

From the above results, it is clear that the isolated product is N-("2'-(3'-
chloro)-thenylmethyl]-N-chloroacet-2-
It was revealed that methyl-6-itudelopylanilide. The yield was 39.6% (3,03X 10-3 mole
)Met.

Synthesis Example 4 N -Cz/ -(a/-methoxy) in Synthesis Example 1
1.81 g (6,14X
10"mole) was used, the reaction was carried out in the same manner as in Synthesis Example 1, the post-treatment was carried out, and the product was purified by column chromatography to obtain a yellow solid 1.13.@. The result of measuring the infrared spectrum of this product. , C-H at 3110-2900cln
Bond-based absorption* 1670c! n-' K7 Mi)
It showed strong absorption based on the cargenyl bond of ' group. Its elemental analysis value is 048.43%, H4.05, N3.
99chi, C15H4, N5OBrC2 (372
,71) is the calculated value for C4B, 20%, H
4.32%.

It was in good agreement with N3.75%.

In addition, when mass spectra were measured, 1. )/.

371 is the molecular ion peak corresponding to the molecular weight.

M", n7e 336 KMe-C2K compatible Surt'-ri-IV/@293 K Me-coca2cz
Furthermore, the bamboo nuclear magnetic resonance spectrum is shown as a specific example in the specification.

From the above results, the isolated product is N-(2'-(5'-from)-thenylmethyl-N-chloroace)-2,
It became clear that it was 6-methylanilide. The yield is N-(2'-(5'-bromo)-chenylmethyl)
-2,6-dimethylaniline, 49.5 To
(3,04×10-'mole).

Synthesis Example 5 The N-substituted-chloroacetanilides listed in Table 1 were synthesized by the same method as described in detail in Synthesis Examples 1-4. Table 1 also abbreviates the aspects, physical properties (boiling point), characteristic absorption values in infrared absorption spectrum, and elemental analysis results of the synthesized N-substituted-chloroacetanilide compounds. The display of the compound in the above-mentioned Synthesis Example 6 1-(α,α-dimethylbenzyl)-3-(2'-chlorobenzyl)urea In a urea Erlenmeyer flask, 18.1 g of α,α-dimethylbenzyl isocyanate and 2-chloro Benzylamine 14.2.p
was added and left at room temperature for 2 hours. The precipitated crystals were recrystallized with ethanol to give 28 colorless crystals with a melting point of 165-166°C.
．． 5g was obtained.

The molecular structure of this product was confirmed to match that of the title compound by INMR.

Synthesis Example 7 1-(α,α-dimethylbenzyl)-3-(2′-bromobenzyl)urea triangular fusco with α,α-zomethylpe/dylisocyanate i s, i g and 2-bromoindylamine 21
．． 2 g was added and left at room temperature for 2 hours. The precipitated crystals were filtered to give 38.117 colorless crystals with a melting point of 181-183°C.
I got it.

Next, Table 2 shows examples of compounds represented by general formula (3).

Formulation Example 1 (Irrigation agent) 9N-(2'-(3'-methoxy)-) obtained in Synthesis Example 1
10 parts of chenylmethyl-N-chloroacetyl-2,6-dimethylanilide, 1-(α, α
-dimethylpencil) 45 parts of a 2:1 mixture of 3-(2'-chloroto (trade name: manufactured by Kuniosha, both clay minerals), 5 parts of Norpol 800 (trade name: manufactured by Toho Chemical Industries) as a surfactant were uniformly mixed and ground to obtain a 5C1 wettable powder.

Formulation Example 2 (Emulsion) N-(2'-(5'-ethoxy)- obtained in Synthesis Example 2)
10 parts of chenylmethylioN-chloroaceto-2,6-dimethylanilide, 1-(α,α- obtained in Synthesis Example 7)
dimethylbenzyl) -3-(2'-bromobenzyl)
30 parts of urea, 40 parts of xylene, and 10 parts of TURZOL 800A as a surfactant were mixed and dissolved to obtain a 50% emulsion.

Formulation Example 3 (granules) 9N-(2'-(3'-chloro)-chenylmethyl)-N-chloroaceto-2-methyl-6- obtained in Synthesis Example 3
3 parts of itzolopyranilide, 1-(α
, α-dimethylbenzyl)-3-(2'-)lifluoromethylpencil) urea ["D: 5 parts, 47 parts of bentonite, 40 parts of coolite, and 5 parts of Tsurpol 800A as a surfactant were uniformly mixed and ground. Water was added and stirred uniformly to form a yeast-like mixture, which was then extruded through a knot hole with a diameter of 0.7 m, dried, and then cut into lengths of 1 to 2111 I to obtain 8-inch granules.

Test Example 1 A 1/8850 are porcelain pot was filled with paddy field soil (alluvial loam) that had been stirred with water, and after sowing paddy weeds, rice seedlings at the 3-leaf stage (variety: Akinishiki) were placed at a depth of 2 The plants were transplanted into a pot and water was added to make them submerged at 3 cy++. Next, predetermined amounts of water diluted water solutions of each compound prepared according to Formulation Example 1 were dropped on the rice seedlings on the 7th and 14th day after transplantation. After treatment, the plants were grown in a greenhouse at an average temperature of 25° C., and the herbicidal effects of each test compound were investigated three weeks later. The results are shown in Table 3. However, the broad-leaved plants shown in the table refer to azaena, azalea, red pepper, etc. The herbicidal effect was evaluated according to the following criteria.

Evaluation value　　　　　　　　Weeding effect 5 Complete control ４　　　　80chi control ３　　　　60chi control 2　　　　40chi control １　　　　　20chi control 0 No effect In addition, paddy rice phytotoxicity was evaluated using the following criteria.

× withering, serious damage, medium harm + small book ± small book - harmless Compounds in Table 3 [ ] indicate the compounds in Table 2, and parentheses indicate those obtained in Synthesis Examples 1 to 4 are compounds A1 to A4, respectively, and compounds I65 and after are shown according to the compounds listed in Table 1, respectively.

″l Test Example 2 1/8850 are field soil (clay loam) in a porcelain pot
and sow various plant seeds to a depth of 0.5 to 10 mm.
Next, a predetermined amount of a water diluted solution of each compound as an irrigation agent prepared according to Formulation Example 1 was sprayed onto the soil surface. After treatment, the plants were grown in a greenhouse at an average temperature of 25°C, and two weeks later, the herbicidal effects of each test compound were investigated.

The investigation results are shown in Table 4 along with comparative examples of control compounds.

Note that the criteria for the herbicidal effect in Table 4 are the same as in Test Example 1.

4. Brief explanation of the figures Figure 1 shows the H-nmr chart of the compound obtained in Synthesis Example 4, Figure 2 shows the IR chart of the compound obtained in Synthesis Example 1, Figures 3 and 4 Figures and Figure 5 are synthesis example 1, respectively.
A chart of H-nmr of the compound obtained in ~3 is shown.

Claims (1)

[Claims] (i) General formula▲ Numerical formula, chemical formula, table, etc.▼ (However, in the formula, A represents a halogen atom, an alkoxy group, or an alkylthio group, R_1, R_2, and R_3
are the same or different hydrogen atoms, halogen atoms,
Indicates an alkyl group, an alkoxy group, and an alkylthio group. ) N-substituted-chloroacetanilide represented by (ii
) A herbicide composition mixed with dibenzylurea represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc.