JPH0669921B2 - Paddy field herbicide - Google Patents

Description

Detailed Description of the Invention

[0001] The present invention is excellent in controlling paddy field weeds with a broader herbicidal spectrum at a reduced application rate, including annual paddy weeds and perennial paddy weeds without the risk of causing chemical damage to paddy rice. It has a good control effect, and in particular, it has an excellent synergistic effect on the control of difficult-to-control perennial paddy weeds such as Cyperus spp., Omodaka, etc., and is also excellent in terms of expanding the suitable application period and extending the weeding period. Regarding a complex herbicide for paddy field which can exhibit an improved control effect, in particular, the following formula (I) N-substituted chloroacetanilide herbicidally active compound which has not been described in the prior art and the known herbicidal active compound of the formula (II) are effective. It relates to a complex herbicide for paddy fields, which is contained as an ingredient.

More specifically, the present invention provides the following formula (I)

[0003]

[Chemical 3]

However, in the formula, A represents a C ₁ -C ₃ alkoxy group, B represents a halogen atom or a C ₁ -C ₃ alkyl group, and l represents a number in the order of 1 to 3, where l Is 2 or 3, a plurality of B may be the same or different, and an N-substituted chloroacetanilide represented by the following formula (II)

[0005]

[Chemical 4]

However, in the formula, Y represents a halogen atom, n represents 0 or an integer of 1 to 3, and when n is 2 or 3, a plurality of Y's may be the same or different. And a tri-substituted phenoxycarboxylic acid anilide represented by the formula: and a complex herbicide for paddy fields.

Although many compounds have been proposed as herbicides for paddy field weeds in the past, despite showing a sufficiently high control activity against paddy field weeds including annual paddy weeds and perennial paddy weeds, It has been extremely difficult to provide paddy field herbicides that do not cause phytotoxicity or other adverse effects on paddy rice.

[0008] Many proposals have been made for paddy field herbicides which attempt to overcome such difficult technical problems by using a combination of a plurality of herbicidally active compounds, but satisfactory results have been obtained. The reality is that there is none.

The present inventors have conducted research to develop a new type of paddy field herbicide capable of overcoming the technical problems of such conventional techniques, particularly the paddy field herbicide.

As a result, a combination of an N-substituted chloroacetanilide compound represented by the formula (I), which has not been described in the conventional literature, with a known herbicidally active compound of the formula (II) is applied to paddy rice. It has been discovered that an excellent herbicidal effect can be achieved for the control of paddy field weeds including annual and perennial paddy weeds with a wide weed spectrum without fear of causing phytotoxicity.

Further, according to the studies by the present inventors, the complex herbicidal paddy field herbicides of the present invention containing the novel herbicidal active compound of the formula (I) and the known herbicidal active compound of the formula (II) as active ingredients. With the achievement of the above-mentioned excellent herbicidal effect, the agent is for the control of perennial paddy weeds that are difficult to control such as Mizuhigai, Omodaka, etc., and furthermore, it exerts a cumulative control effect on Urikawa against annual paddy weeds. The same herbicidal effect was also shown for perennial paddy weeds,
It also shows various improvement benefits such as the appropriate application period of the drug, which can be expanded at a low application rate up to about 15 days after transplanting rice (rice planting), and the advantage of showing a long-lasting medicinal effect with a low application rate. It was discovered that it is an excellent paddy herbicide that can be used.

Accordingly, it is an object of the present invention to provide a new type of complex herbicide for paddy fields. These and many other objects and advantages of the present invention will become more apparent from the description below.

One of the essential components of the complex herbicide for paddy field of the present invention is N represented by the following formula (I) which has not been described in any conventionally known document.
A substituted chloroacetanilide.

[0014]

[Chemical 5]

In the formula, A represents a C _{1 to} C ₃ alkoxy group, B represents a halogen atom or a C _{1 to} C ₃ alkyl group, 1 represents an integer of 1 to 3, and 1 represents 2 Alternatively, in the case of 3, a plurality of Bs may be the same or different.

Regarding the N-substituted-chloroacetanilide compounds including the compound of formula (I), the method for producing the same and the use as a herbicide, Japanese Patent Application No. 58- No. 111077 (filed on June 22, 1983) is disclosed in detail.

The other essential component of the complex herbicide for paddy field of the present invention is a known herbicidally active compound of the following formula (II).

[0018]

[Chemical 6]

However, in the formula, Y represents a halogen atom, n represents 0 or an integer of 1 to 3, and when n is 2 or 3, a plurality of Y's may be the same or different. A tri-substituted phenoxycarboxylic acid anilide represented by:

The herbicides containing the compound of formula (II) as an active ingredient are disclosed in detail in JP-A-57-171904.

The compound of the formula (I) is, for example, the following formula (2)

[0022]

[Chemical 7]

However, in the formula, A, B and l have the same meanings as described for formula (I), and a compound represented by the following formula (3)

[0024]

## STR00008 ## ClCH ₂ COX (3) In the formula, X represents a halogen atom, and it can be produced by reacting with a chloroacetyl halide.

In the reaction, the compound of formula (2) and the compound of formula (3)
The charged molar ratio of the compound can be appropriately selected, for example,
It is general to use the compound of the formula (3) in an equimolar amount or a slight excess amount with respect to the compound of the formula (2). Since hydrogen halide produced as a by-product of the reaction causes a decrease in the yield of the product, it is preferable to carry out the reaction in the presence of a hydrogen halide scavenger in the reaction system. Examples of such scavengers include, for example, trimethylamine,
Examples are trialkylamines such as triethylamine and tripropylamine; pyridine; sodium alcoholate; sodium carbonate.

The reaction is preferably carried out in the presence of a suitable organic solvent, and examples of such a solvent include benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, ethylene chloride and the like. Aliphatic or aromatic hydrocarbons or halogenated hydrocarbons; ethers such as diethyl ether, dioxane and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile;
Examples are N, N-dialkylamides such as N, N-dimethylformamide and N, N-diethylformamide; dimethylsulfoxide and the like.

In carrying out the reaction, the order of addition of the reaction raw materials is not particularly limited, but in general, the compound represented by the formula (2) is dissolved in a solvent, charged into a reactor and dissolved in the solvent of the formula (3). Acetylhalogenide is preferably added with stirring. Of course, it is also possible to continuously add the raw materials to the reaction system and continuously take out the produced reaction product from the reaction system.

The temperature in the above reaction can be selected from a wide range, for example, -20 ° C to 150 ° C, more preferably 0 ° C to.
A range of 120 ° C can be exemplified. The reaction time can be appropriately changed depending on the type of raw material, but for example, 5 minutes to
The range may be 10 days, preferably 1 to 40 hours. The reaction is preferably carried out under stirring conditions.

There are no particular restrictions on the method of isolating and purifying the desired product, that is, the compound of formula (I) from the reaction system, and known methods can be appropriately selected and employed. For example, it is possible to employ a means of cooling the reaction liquid or allowing it to cool naturally, returning it to or near room temperature, distilling off the reaction solvent and the remaining hydrogen halide scavenger, and then extracting the residue with benzene. By the above operation, a salt and a high molecular weight compound produced from the by-produced hydrogen halide and the hydrogen halide scavenger can be separated. For the benzene layer,
For example, the target compound of formula (I) can be obtained by drying with a desiccant such as Glauber's salt or calcium chloride, distilling off benzene, and subjecting the residue to vacuum distillation. In addition to isolation and purification by vacuum distillation, purification by chromatography, or when the product is a solid, can be performed by recrystallization from a solvent such as hexane.

According to another embodiment, the compound of formula (I) is represented by the following formula (4):

[0031]

[Chemical 9]

However, in the formula, A has the same meaning as described in formula (I), X represents a halogen atom, and a 2-substituted thiophene compound represented by the following formula (5)

[0033]

[Chemical 10]

However, in the formula, B and l can also be produced by reacting with chloroacetanilide represented by the same meaning as described for formula (I).

The substituted thiophene and chloroacetanilide used as raw materials may be obtained by any method. The conditions for carrying out the reaction and the isolation and purification method are the same as those of the compound of formula (2) and formula (3) described above.
The conditions used in the reaction with chloroacetylhalogenide and the conditions similar to the isolation and purification method can be adopted.

In the complex herbicide for paddy field of the present invention, examples of the group A in the compound of formula (I) which has not been described in the prior art and which can be produced, for example, as described above are methoxy, ethoxy and n- or Mention may be made of C ₁ -C ₃ alkoxy groups such as iso-propoxy, examples of groups B being halogen atoms such as Cl, Br, F, I and C such as methyl, ethyl and n- or iso-propyl. it can be exemplified ₁ -C ₃ alkyl group.

Among such compounds of formula (I), A in formula (I) represents a —OCH ₃ group, and B represents —Cl, —C.
Compounds having a group selected from the group consisting of H ₃ and —C ₂ H ₅ and having 1 as 2 are preferred. In formula (I), A is a 3′-OCH ₃ group and B is 2,6-dimethyl. More preferred are compounds that are groups ( l = 2).

Examples of such compounds of formula (I) are:
The compounds shown in Table 1 below can be exemplified, and as more preferable examples, the following compounds can be exemplified.

N- [2 '-(3'-methoxy) -thienylmethyl] -N-chloroaceto-2,6-dimethylanilide [in the formula (I), A = 3'-methoxy, B = 2,6-
Dimethyl, l = 2] (Compound of Reference Example 1 below), N-
[2 '-(3'-methoxy) -thienylmethyl] -N-
Chloroaceto-2-chloro-6-methylanilide [in formula (I), A = 3′-methoxy, B = 2-chloro and 6
-Methyl, l = 2] (No. 14 compound in Table 1 below),
N- [2 '-(5'-methoxy) -thienylmethyl]-
N-chloroaceto-2,6-dimethylanilide [in the formula (I), A = 5'-methoxy, B = 2,6-dimethyl, l = 2] No. 5 compound in Table 1 below, N- [2 ′-
(3′-methoxy) -thienylmethyl] -N-chloroaceto-2-ethyl-6-methylanilide [in the formula (I),
A = 3′-methoxy, B = 2-ethyl and 6-methyl,
1 = 2] No. 12 compound in Table 1 below.

In the composite herbicide for paddy field of the present invention, among the above-mentioned known compounds of the formula (II), the compound in which n is 0 (unsubstituted) is more preferable.

2- (2,4-dichloro-3-methyl-phenoxy) propionanilide can be exemplified as a particularly preferable compound of the formula (II).

The complex herbicide for paddy field of the present invention comprises at least one compound of formula (I) N-substituted chloroacetanilide which has not been described in the above-mentioned publicly known literature, and a compound of formula (II) which is a known herbicidal active compound as described above. The compound (1) and the compound (2) are contained as active ingredients, but the ratio of the compound (or combination) of the compound of the formula (I) and the compound of the formula (II) can be appropriately selected and changed. For example, compound of formula (I): compound of formula (II) (weight ratio) = 1: 0.05 to 15, more preferably 1:
A composite ratio such as 0.1 to 7, particularly preferably 1: 0.5 to 3, can be exemplified.

The complex herbicide for paddy field of the present invention can be used as it is or as an appropriate composition with a suitable gas, liquid or solid carrier or diluent, and other additives or auxiliary agents. When used in the form of such a composition, it can be used in the form of various dosage forms by utilizing a method for preparing a pesticide formulation known per se. The compound of the formula (I) and the compound of the formula (II) and / or the formula (III) can also be used in the form of being mixed in situ or applied in combination. Examples of the above various dosage forms include any desired dosage form such as powder, granules, tablets, liquids, emulsions, wettable powders, oils, aerosols and smokers.

Carriers and diluents used for such preparations, and other additives and auxiliaries are well known in the art, and can be appropriately selected and used in the present invention.

Examples of such solid carriers or diluents include clays represented by kaolinite group, montmorillonite group or attapulgite group; talc, mica,
Inorganic substances such as pyrophyllite, pumice, vermiculite, gypsum, calcium carbonate, diatomaceous earth, magnesium lime, apatite, zeolite, anhydrous silicic acid; soybean flour, wheat flour, crystalline cellulose and other plant organic substances; or petroleum resin, Examples thereof include synthetic or natural polymer compounds such as polyvinyl chloride, polyalkylene glycol, ketone resins, ester gum, and cobal gum; or solid carriers or diluents such as urea.

As the liquid carrier or diluent, any liquid which can disperse or dissolve the compound of the present invention with an auxiliary agent can be used even if it is a solvent or a non-solvent. For example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and methylnaphthalene; carbon tetrachloride, chloroform, trichloroethylene, monochloro benzene,
Chlorinated hydrocarbons such as o-chlorobenzene; dioxane,
Ethers such as tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, isophorone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, diethyl succinate; methanol, n-hexanol, ethylene Alcohols such as glycol and diethylene glycol; ethers such as ethylene glycol ethyl ether, diethylene glycol ethyl ether and diethylene glycol butyl ether; liquid carriers and diluents such as dimethylformamide and dimethylsulfoxide.

Further, examples of the gas carrier or diluent include:
Propellant gases for aerosols such as fluorotrichloromethane, dichlorodifluoromethane, 1,
2-dichlorotetrafluoroethane etc. can be illustrated.

In addition to the above, a surfactant and other auxiliary agents can be used for the purpose of enhancing the emulsification, dispersion and spreadability of the composite active ingredient used in the present invention. As the surfactant, for example, any of nonionic, anionic, and cationic can be used, but nonionic and anionic ones are usually used. Suitable nonionic surfactants include those obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol, and alkylphenols and alkyls such as isooctylphenol, nonylphenol, octylnaphthol and butylnaphthol. Polymerized addition of ethylene oxide to naphthol, polymerized addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid, polymerization of ethylene oxide to amines such as dodecylamine and stearic acid amide, stearyl Examples thereof include those obtained by polymerizing and adding ethylene oxide to mono- or dialkyl phosphoric acid such as phosphoric acid and dilauryl phosphoric acid. Examples of the anionic surfactant include sodium lauryl sulfate, alkyl sulfate ester salts such as oleyl alcohol sulfate ester amine salt, sodium sulfone succinate dioctyl ester salt, alkyl sulfonate salts such as sodium 2-ethylhexenesulfonate, and the like. Examples thereof include aryl sulfonates such as sodium isopropyl naphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.

The above carriers or diluents and additives or auxiliaries can be used individually or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the place of application and the like.

The composite herbicide for paddy field of the present invention can be applied in combination with other herbicides or as a composite herbicide, and can often exert a complementary effect. Furthermore, in order to reduce the number of times of application of the agrochemical, it can be used as a mixture with other agrochemicals such as insecticides, fungicides, plant growth regulators or in combination with them. It can also be used by mixing with fertilizers, soil conditioners and the like.

As described above, the complex herbicide for paddy field according to the present invention is a broad herbicidal composition including annual paddy field weeds and perennial paddy field weeds at a reduced application rate without fear of causing chemical damage to paddy rice. It has a spectrum and can exert an excellent control effect on the control of paddy weeds.

Examples of such paddy weeds are narrow-leaved weeds such as Taenia cinerea, Prunus chinensis, Kouenubie, Kogomegayatsu, etc., and annual weeds such as broad-leaved weeds such as eel, azena, yellow sedge, scutellaria, abnomome, Oabu nome, Misohakobe, and the like. Firefly, pineapple,
Illustrative are narrow-leaf weeds such as Mizuhigai and perennial paddy weeds such as broad-leaved weeds such as Urikawa, Omodaka, Heraomodaka, Azemushiro and Hirumushiro. In particular, it has an excellent addition effect at a low application rate for the control of difficult-to-control perennial paddy weeds such as Mizuhigai, Omodaka and Urikawa, and is also excellent in terms of extending the suitable application period and extending the weeding period. The improved control effect can be demonstrated.

The composite herbicide for paddy field of the present invention is effective for controlling paddy field weeds as exemplified above at a low application rate, exhibits selective herbicidal activity that does not cause phytotoxicity to paddy rice, and has a suitable application period. Can be expanded. For example, the combined use can expand the suitable application period up to about 15 days after transplanting rice (rice planting).
It can be applied to the direct-seeded paddy rice with the same expanded application period. Furthermore, the combined use can achieve an improvement effect in which the medicinal effect persistence with an extended weeding period and the advantage of showing a low application rate are obtained. The composite herbicide for paddy fields of the present invention is
Along with the combined use improving effect, it is possible to show a cumulative controlling effect on perennial paddy field weeds that are difficult to control, such as Mizuhaya-tsui, Omodaka, Urikawa, and the like. There is a benefit that can be exhibited without fear of being accompanied by.

The application amount of the complex herbicide for paddy field of the present invention can be appropriately selected and changed according to the kind of weeds for its control, application time, application site or area, weather and other natural environment conditions. A compound of formula (I) and formula (II)
The total amount of active compounds consisting of compounds is, for example, 1 g
˜3 kg / 10a, preferably 5 g to 1 kg / 10a,
More preferably, an application amount such as 10 g to 400 g / 10a can be exemplified.

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

[0056]

EXAMPLES Production Example 1 [Compound of formula (I)] N- [2 '-(3'-methoxy) -thienylmethyl]-
2,6-dimethylaniline 5.81 g (0.024 mol)
e) is dissolved in 40 ml of benzene and triethylamine 3.
10 g (0.031 mole) was added, and the mixture was placed in ice water. Next, 3.19 g (0.02 g) of chloroacetyl chloride
15 ml of benzene solution (8 mole) was gradually added. After stirring for 3 hours, the mixture was heated at 50 ° C. for 3 hours. The reaction mixture was cooled to room temperature, washed successively with 50 ml of water, 50 ml of 2N-hydrochloric acid and then 50 ml of water, and the benzene layer was dried over anhydrous sodium sulfate. After distilling off benzene under reduced pressure, the residue was vacuum distilled to give a boiling point of 172 ° C /
5.03 g of a pale yellow solid of 0.15 mmHg was obtained. As a result of measuring the infrared spectrum of this compound is as shown in FIG. 1, absorption based on C-H bond in 3100～2800Cm ^-1, it showed strong absorption based on the carbonyl bond of the amido group in 1670 cm ^-1.

The elemental analysis values are C59.20%, H5.
64%, N 4.37%, composition formula C ₁₆ H ₁₈ NSO ₂
C59.33 which is the calculated value for Cl (323,84)
%, H5.61%, N4.33%.

When the mass spectrum was measured,
Molecular ion peak corresponding to molecular weight at m / e 323, M
⁺ , A peak corresponding to M ⁺ -Cl at m / e 288, m / e
A peak corresponding to M ⁺ -COCH ₂ Cl at 246, m / e
To 127 (100%)

[0059]

[Chemical 11]

The respective peaks corresponding to are shown.

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ; ppm: tetramethylsilane standard, deuterated chloroform solvent) is shown in FIG. The analysis results are as follows.

[0062]

[Chemical 12]

A single line for 6 protons is shown at 1.95 ppm and corresponds to the methyl proton of (f) substituted at the 2 and 6 positions of the phenyl group. Proton 3 at 3.50 ppm
This shows a single line corresponding to the number of single lines and corresponds to the methyl proton in (a). Shows a single line of two protons at 3.72 ppm,
This corresponds to the methylene proton of (e). 4.75ppm
Shows a single line of two protons, which corresponds to the methylene proton of (d). A quartet for two protons is shown at 6.55 ppm, which corresponds to the protons of the thiophene ring in (b) and (c). Proton 3 at 7.00 to 7.45 ppm
The number of multiple lines is shown and corresponds to the protons of the benzene ring in (g), (h), and (i).

From the above results, the isolated product is N- [2 '
It was revealed to be-(3'-methoxy) -thienylmethyl] -N-chloroaceto-2,6-dimethylanilide. The yield was 6 with respect to N- [2 '-(3'-methoxy) -thienylmethyl] -2,6-dimethylaniline.
It was 6.2% (0.016 mole).

Production Example 2 [Compound of formula (I)] 2.71 g of 2,6-diethyl-N-chloroacetanilide
(0.012 mole), 2-chloromethyl-5-ethoxythiophene (2.12 g, 0.012 mole) and potassium carbonate (0.83 g, 6.0 × 10 ⁻³ mole) were added to N, N.
-Dimethylformamide (hereinafter abbreviated as DMF) 50
It was added to ml and stirred. The reaction mixture at 100 ° C. for 3
After heating for an hour, the mixture was stirred at room temperature for 1 hour. After the precipitated potassium chloride was filtered off, DMF in the filtrate was distilled off under reduced pressure, 100 ml of water was added to the residue, and the mixture was extracted with ether. After drying the ether layer over anhydrous sodium sulfate, the ether was distilled off under reduced pressure. The residue was vacuum distilled to obtain 3.50 g of a yellow viscous liquid having a boiling point of 182 ° C./0.30 mmHg. When the infrared spectrum of this product was measured, it was 3
Absorption based on C—H bond at 100 to 2800 cm ⁻¹ , 1
It showed strong absorption at 670 cm ^{-1 due} to the carbonyl bond of the amide group. Its elemental analysis value is C62.21%, H6.
61%, N 3.90%, composition formula C ₁₉ H ₂₄ NSO ₂
C62.36 which is the calculated value for Cl (365.92)
%, H 6.62%, N 3.84%.

When the mass spectrum was measured,
Molecular ion peak corresponding to molecular weight at m / e 365, M
⁺ , M / e 330, peak corresponding to M ⁺ -Cl, m / e
Peak corresponding to M ⁺ -COCH ₂ Cl at 288, m / e
To 141 (100%)

[0067]

[Chemical 13]

The respective peaks corresponding to are shown.

Further, the result of measurement of ¹ H-nuclear magnetic resonance spectrum (δ; ppm: tetramethylsilane standard, deuterated chloroform solvent) is shown in FIG.

The analysis results are as follows.

[0071]

[Chemical 14]

A triple line corresponding to 6 protons is shown at 1.15 ppm, which corresponds to the methyl proton (h) of the ethyl group substituted at the 2,6-position of the phenyl group. A triple line corresponding to three protons is shown at 1.40 ppm, which corresponds to the methyl proton of (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 (g) methylene proton of the ethyl group substituted at the 2,6-position of the phenyl group. A single line corresponding to two protons is shown at 3.66 ppm, which corresponds to the methylene proton of (f). A quartet for two protons is shown at 4.04 ppm,
This corresponds to the methylene proton of (b) of the ethoxy group substituted on the thiophene ring. A single line with two protons is shown at 4.75 ppm and corresponds to the methylene proton of (e) adjacent to the thiophene ring. Proton 1 at 5.95 ppm
The number of double lines is shown and corresponds to the proton of (c) on the thiophene ring. A double line for one proton is shown at 6.39 ppm, which corresponds to the proton (d) on the thiophene ring. Multiple lines appear at 7.10 to 7.40 ppm, (i),
It corresponds to the proton of the benzene ring in (j) and (h).

From the above results, the isolated product is N- [2 '
It was found to be-(5'-ethoxy) -thienylmethyl] -N-chloroaceto-2,6-diethylanilide. The yield was 79.7% (9.57 × 10 ⁻³ mole) based on 2,6-diethyl-N-chloroacetanilide.
It was.

Production Example 3 [Compound of Formula (I)] N-substituted-chloroacetanilide shown in Table 1 below was synthesized by the same method as described in detail in Production Examples 1 and 2. Table 1 shows the synthesized N-substitution-
The mode of the chloroacetanilide compound, the physical properties (boiling point), the characteristic absorption value in the infrared absorption spectrum, and the elemental analysis result are also summarized.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

Test Example 1 Flooded Soil Treatment Test (1) Test Method Paddy soil was placed in a pot of 1/5000 are and put in a state of scavenging, and then a seed of Novier, eel, yellow cypress and firefly seeds were sown in each pot. In addition, four tubers of Urikawa and Mizuhigayuri were transplanted in groups of four. In addition, two 2-leaf stage rice plants were transplanted as one strain, and three strains were transplanted. The chemical treatment was carried out 10 days and 15 days after seeding with a fixed amount of the wettable powder of the composite agent of the present invention (according to Formulation Example 1), and then the pots were allowed to stand in a greenhouse to remove 1 of each weed. I trained for months. The herbicidal activity against each weed and the phytotoxicity against rice were determined according to the following criteria. The results are shown in Table 2.

[0079] The table also shows the results of the tests and evaluations as described above except that each single agent was used as a control example. In the table, the symbols in the compound column are as follows.

I- (1): N- [2 '-(3'-methoxy) -thienylmethyl] -N-chloroaceto-2,6-
Dimethylanilide I- (2): N- [2 '-(3'-methoxy) -thienylmethyl] -N-chloroaceto-2-chloro-6-methylanilide II: 2- (2,4-dichloro-3-) Methyl-phenoxy) propionanilide

[0081]

[Table 4]

Test Example 2 After paddy soil was placed in a substituting state in a pot of 1 / 5,000 are, 200 seeds of firefly seeds were sown within 1 cm of the surface layer while being mixed with the soil. Then, when the pot was left standing in a greenhouse and the firefly became 2 L (15 days after making the pot), the same wettable powder as in Test Example 1 was used, each of them was treated individually and in combination, and after the chemical treatment, The individual that remained after 30 days was extracted and the air-dry weight was determined. The results are shown in Table 3.

[0083]

[Table 5]

Test Example 3 Outdoor Pot Test A paddy soil was placed in a square-shaped concrete pot of 50 cm × 50 cm which was left outdoors, and each pot was sown with a certain amount of Novier, Kokonagi, Kishigusa, and Firefly seeds, and also with pine nuts. Six overwintering strains were planted, and six Urikawa, Omodaka, and Cyperus tuber tubers were planted. Further 2.
4 strains were transplanted with 5 ^L of rice as one strain. On the 15th day after pot preparation (Novier 2 to 2.5 ^L ), 2 k per 10 ares of single and mixed granules prepared according to Preparation Example 3
g, 4 kg. 4 after drug treatment
After 5 days, the herbicidal activity and phytotoxicity against each weed were discriminated according to the criteria of Test Example 1, and the results are shown in Table 4.

[0085]

[Table 6]

Formulation Example 1 (Emulsion) N- [2 '-(3'-methoxy) -thienylmethyl] -N-chloroaceto-2-chloro-6-methylanilide 10 parts 2- (2,4-dichloro-3) -Methyl-phenoxy) propionanilide 10 parts xylene 55 parts cyclohexanone 15 parts polyoxyethylene alkylallyl ether 10 parts were mixed and dissolved to obtain an emulsion.

Formulation Example 2 (Granule) N- [2 '-(5'-methoxy) -thienylmethyl] -N-chloroaceto-2,6-dimethylanilide 1 part 2- (2,4-dichloro-3-) Methyl-phenoxy) propionanilide 1 part Bentonite: talc (2: 1 mixture) 93 parts Sodium lignin sulfonate 5 parts After mixing and pulverizing, granules are obtained by a usual pesticide formulation method.

[Brief description of drawings]

1 is an infrared absorption (ir) chart of the compound of formula (I) obtained in Production Example 1. FIG.

FIG. 2 is its ¹ H-nuclear magnetic resonance ( ¹ H-nmr) chart.

FIG. 3 shows ^{1 of the} compound of formula (I) obtained in Production Example 2.
H-nmr chart.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kiyoshi Sugaya 1315 Wakaguri, Ami-cho, Inashiki-gun, Ibaraki Sanryo Yuka Co., Ltd. Central Research Laboratory

Claims (4)

[Claims] 1. The following formula (I): However, in the formula, A represents a C _{1 to} C ₃ alkoxy group, B represents a halogen atom or a C _{1 to} C ₃ alkyl group, and 1 represents 1 to 1
And an N-substituted chloroacetanilide represented by the following formula (II): wherein l is 2 or 3, and a plurality of Bs may be the same or different. ] However, in the formula, Y represents a halogen atom, and n is 0 or 1.
To 3 in which, when n is 2 or 3, a plurality of Y's may be the same or different, and a tri-substituted phenoxycarboxylic acid anilide represented by A complex herbicide for paddy fields, which is characterized by containing. 2. In the compound of formula (I), A in formula (I) represents a —OCH ₃ group, and B represents —Cl, —CH ₃ and —.
The compound herbicide for paddy fields according to claim 1, which is a compound showing a group selected from the group consisting of C ₂ H ₅ and 1 being 2. 3. In the compound of formula (II), the compound of formula (I
The compound according to claim 1, wherein n in I) is 0.
Item or the complex herbicide for paddy according to item 2. 4. The compounding ratio of the compound of formula (I) and the compound of formula (II) is as follows: compound of formula (I): compound of formula (II) (weight ratio) = 1:
The composite herbicide for paddy fields according to any one of claims 1 to 3, which is 0.05 to 15.